Compositions useful for oil extraction

ABSTRACT

The present invention relates to compositions comprising a plant material, and methods for using the same in extracting or removing a hydrocarbon-containing substance from a substrate or remediating a substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of International Patent ApplicationNo. PCT/US2012/059770, filed on Oct. 11, 2012, which claims the benefitof U.S. Provisional Patent Application No. 61/545,817, filed on Oct. 11,2011, each of which is incorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates to compositions comprising plant material,and methods for using the same to extract a hydrocarbon-containingsubstance such as oil, coal tar, creosote, sludge, bitumen or refinedproducts thereof from a substrate or to remediate a substrate such assand, soil, rock, sediment, metal, glass, porcelain, concrete or water.

BACKGROUND

World petroleum supplies are finite. Thus, as world petroleum demand hasincreased (84,337 M bpd worldwide in 2009; US Energy InformationAdministration), easily accessible reserves have been depleted.Furthermore, much of the world's proven conventional petroleum reservesare located in regions which are politically unstable. Accordingly,supplies of petroleum from such regions might be uncertain sinceproduction of petroleum or the transportation of petroleum products fromsuch regions might be interrupted.

Bituminous sands, colloquially known as oil sands or tar sands, are atype of unconventional petroleum deposit. The sands typically comprisenaturally occurring mixtures of sand, clay, water, and a dense andviscous form of petroleum known as bitumen. Oil sands reserves have onlyrecently been considered to be part of the world's oil reserves, ashigher oil prices and new technology enable oil sands to be profitablyextracted and refined. Thus, oil sands are now a viable alternative toconventional crude oil. Oil sands might represent as much as two-thirdsof the world's total “liquid” hydrocarbon resources, with at least 1.7trillion recoverable BOE (barrel of oil equivalent) in the CanadianAthabasca oil sands alone.

Extra-heavy oil and bitumen flow very slowly, if at all, towardoil-producing wells under normal reservoir conditions. Accordingly, incertain oil recovery operations from oil sands, the oil is made to flowinto wells by using in situ techniques that reduce its viscosity byinjecting steam, solvents, or hot air into the sands. These processestypically use large amounts of water and require large amounts of energyrelative to conventional oil extraction. Further, typical extractionprocesses applied to oil sands generate significantly higher amounts ofgreenhouse gases per barrel relative to the production of conventionaloils due to the increased energy requirements for recovery of oil fromoil sands.

In other oil sand mining operations, where oil sands are relativelyclose to the earth's surface, surface mining has been used to extractthe oil contained therein. After removing the overburden (the soilcovering the oil sands), the sands are mechanically excavated andtransported to a refining facility.

In one surface-mining method, after excavation, hot water and causticsoda (NaOH) are added to the sand. The resultant slurry is piped to theextraction plant where it is agitated and oil is skimmed off themixture. The combination of hot water, sodium hydroxide, a flocculantand agitation generally releases bitumen from the oil sand, and the oilfloats to the top of separation vessels where it is separated. Then, theseparated oil is further treated to remove residual water and finesolids before subsequent processing to convert the heavy oil to usableproducts.

Such conventional processes to extract oil from oil sands also employmixing the oil sand with high pH water, and then aerating the resultantmixture with air to produce froth (see, e.g., Masliyah, J.; Zhou, Z. J.;Xu, Z.; Czarnecki, J.; Hamza, H.: “Understanding water-based bitumenextraction from Athabasca oil sands.” The Canadian Journal of ChemicalEngineering 2004, 82, (4), 628-654). A slurry of high pH water and oilsand is placed in a primary separation cell (PSC). Agitation andintroduction of air assists in separating oil from the oil sand, andcreates a froth in which the oil is entrained. The froth is removed,deaerated, and sent to feed tanks for further treatment. The remainingsand, comprising residual oil not removed in the PSC, is treated as“middlings” or as bottoms using the same process for extracting oil fromoil sands in the PSC (i.e., high pH water and aeration). The froth fromthese subsequent processes is recycled to the PSC. The overallenhancement of oil from the oil in the froth is approximately 60% bymass over the iterative removal steps.

About two tons of oil sands are required to produce one barrel (roughly⅛ of a ton) of oil. After oil extraction, the spent sand and othermaterials are typically transported back to the mine for disposal.However, even with improved extraction processes, up to 10% of the oilin the oil sands can be left in the resultant tailings. Thus, theprocess is inefficient. The tailings can contain significant amounts ofoil and other pollutants which must be disposed of in an environmentallysound manner. In conventional oil sand mining operations, this hasresulted in large lagoons containing high levels of oil and otherpollutants. Accordingly, there is a need for improved compositions andmethods for extraction of oil from oil sands that are more efficient(e.g., can remove higher amounts of oil), use less energy, and producetailings that are environmentally benign.

In addition, in conventional oil production processes, methods ofenhancing oil recovery are known. These include, but are not limited tohydraulic fracturing of rock formations containing hydrocarbon deposits.In hydraulic fracturing operations, a fluid (e.g., water) which cancomprise various additives (e.g., acids, rheology modifiers, detergents,gels, gas, proppant, etc.) is introduced into a rock formation underhigh pressure to fracture the rock formation. Such fracturing of ahydrocarbon-bearing rock formation effectively increases the surfacearea of rock exposed to a wellbore (i.e., along the fracture faces), andaccordingly, allows more hydrocarbon to flow into the well bore.However, the viscosity of the oils contained in the formation can limitthe utility of hydraulically fracturing rock formations which containheavy oils. That is, if the viscosity of the oil is too high, increasingthe surface area of the formation exposed to the well bore along thefracture might not significantly increase production rates. Accordingly,there is a need for hydraulic fracturing fluids which can enhance totaloil recovery or increase oil production rates.

In addition, remediation of environmentally compromised sites (e.g.,hazardous waste sites) is an ongoing challenge. For example, there aremany sites where hydrocarbons (e.g., crude oil, coal tar, creosote,refined oil products) have been spilled or discharged into theenvironment. Such discharges can result in contamination of soil orwater, and can contaminate groundwater supplies. Accordingly, suchcontaminated sites or waters (e.g., rivers, streams, ponds and harbors)require remediation to extract contaminants.

There are several known remediation technologies. One method comprisesexcavation of contaminated soil. However, remediation by excavation hastraditionally been a “dig and haul” process, wherein contaminated soilsare excavated and disposed of in landfills or destroyed by thermaltreatments such as incineration. In the case of landfill disposal ofcontaminated soil, the problem of soil contamination is not resolved asthe soil is relocated and moved to another location. In the case ofthermal desorption, the hydrocarbon or other pollutants can bedestroyed, but typically produces a large carbon footprint, which, inand of itself, is not an environmentally friendly process, since energyis required and greenhouse gases are produced.

Chemical treatment (e.g., oxidation) has also been utilized in theremediation of contaminated soil. This process comprises excavation ofthe contaminated soil, followed by chemical treatment to chemicallymodify or degrade the pollutants to potentially less toxic or hazardousforms. However, such methods can require large quantities of specializedchemicals to oxidize the contaminants, and can be ineffective atoxidizing certain pollutants.

Another remediation method comprises injection of a material into thesoil to sequester contaminants, with a goal of immobilizing them andpreventing them from migrating. For example,stabilization/solidification (S/S) is a remediation or treatmenttechnology that relies on the reaction between a binder and soil tostop, prevent or reduce the mobility of contaminants. Stabilizationcomprises the addition of liquid or solid materials to contaminated soilto produce more chemically stable constituents. Solidification comprisesthe addition of liquid or solid reagents to a contaminated material toimpart physical, for example, dimensional stability, so that they areconstrained in a solid product and to reduce mobility of thecontaminants. However, such methods might not be desirable since overtime, the solids can break down or degrade, releasing the hydrocarbonsor other pollutants back into the environment.

Accordingly, there is a need for cost-effective methods for extractingcontaminants (e.g., hydrocarbons) from soils and other substrates atenvironmentally compromised or contaminated sites and for sequesteringcontaminants in situ in a cost effective manner.

SUMMARY OF THE INVENTION

The present invention provides aqueous compositions comprising about 1wt % to about 50 wt % of plant material, 0 to about 20 wt % of apolysaccharide, 0% to about 10 wt % of an alcohol, 0% to about 15 wt %of a base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of anacid, 0% to about 10 wt % of an additive, and about 10 wt % to about 95wt % of water, wherein the aqueous composition has a pH of from about 9to about 13.

The present invention further provides extractants comprising about 0.1wt % to about 2 wt % of plant material, 0 to about 2 wt % of apolysaccharide, 0% to about 1 wt % of an alcohol, 0% to about 10 wt % ofa base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of an acid,0% to about 10 wt % of an additive, and about 90 wt % to about 99.9 wt %water. The aqueous compositions and extractants are useful forextracting a hydrocarbon-containing substance from a substrate or forremediating a substrate.

The present invention further provides substantially anhydrouscompositions comprising about 20 wt % to about 99.9 wt % of plantmaterial, 0 to about 20 wt %, of a polysaccharide, 0% to about 1 wt % ofan alcohol, 0% to about 50 wt % of a base, 0% to about 10 wt % of asalt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and 0% to about 10 wt % water. The aqueous compositions andextractants can be dried to form substantially anhydrous compositions,which are useful for convenient handling or storage.

The present invention also provides methods for extracting ahydrocarbon-containing substance from a substrate, comprising contactingthe substrate with an aqueous composition or extractant of the inventionunder conditions effective for extracting at least some of thehydrocarbon-containing substance from the substrate.

The present invention further provides methods for remediating asubstrate, comprising contacting the substrate with an aqueouscomposition or extractant of the invention under conditions effectivefor remediating the substrate.

The present invention further provides hydraulic fracturing fluidscomprising an aqueous composition or extractant of the invention.

The present invention also provides methods for extracting ahydrocarbon-containing substance from a substrate, comprisinghydraulically fracturing the substrate with a hydraulic fracturing fluidof the invention.

The present invention also provides methods for making a substantiallyanhydrous compositions comprising about 20 wt % to about 99.9 wt % ofplant material, 0 to about 20 wt %, of a polysaccharide, 0% to about 1wt % of an alcohol, 0% to about 50 wt % of a base, 0% to about 10 wt %of a salt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and 0% to about 10 wt % water, comprising removing water froman aqueous composition of the invention.

The present invention also provides methods for making substantiallyanhydrous compositions comprising about 20 wt % to about 99.9 wt % ofplant material, 0 to about 20 wt %, of a polysaccharide, 0% to about 1wt % of an alcohol, 0% to about 50 wt % of a base, 0% to about 10 wt %of a salt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and 0% to about 10 wt % water, comprising removing water froman extractant of the invention.

The present invention also provides methods for preparing extractantscomprising about 0.1 wt % to about 2 wt % of plant material, 0 to about2 wt % of a polysaccharide, 0% to about 1 wt % of an alcohol, 0% toabout 10 wt % of a base, 0% to about 10 wt % of a salt, 0% to about 10wt % of an acid, 0% to about 10 wt % of an additive, and about 90 wt %to about 99.9 wt % water, comprising adding water to an aqueouscomposition of the invention.

The present invention also provides methods for preparing extractantscomprising about 0.1 wt % to about 2 wt % of plant material, 0 to about2 wt % of a polysaccharide, 0% to about 1 wt % of an alcohol, 0% toabout 10 wt % of a base, 0% to about 10 wt % of a salt, 0% to about 10wt % of an acid, 0% to about 10 wt % of an additive, and about 90 wt %to about 99.9 wt % water, comprising adding water to a substantiallyanhydrous composition of the invention.

The present invention also provides methods for preparing aqueouscompositions of the invention comprising admixing with water asubstantially anhydrous composition of the invention.

The present invention further provides laundry detergents comprising theaqueous composition of the invention, an extractant of the invention, ora substantially anhydrous composition of the invention.

The present invention further provides methods for removing ahydrocarbon-containing substance from fabric comprising contacting thefabric with a laundry detergent of the invention.

The present invention also provides methods for precipitating finescontained in a vessel further containing a hydrocarbon-containingmaterial and an aqueous composition of the invention or an extractant ofthe invention, the methods comprising acidifying the contents of saidvessel to a pH of about 4.6 or less.

The present aqueous compositions, extractants, substantially anhydrouscompositions (each being a “Composition of the Invention”) and methods,and advantages thereof, are further illustrated by the followingnon-limiting detailed description and Examples.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-B are photographs showing a side view of the vessel containingthe mixture of Example 3 after 60 min of stirring, then briefly allowingthe mixture to settle (FIG. 1A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 1B), also after 60 min ofstirring.

FIGS. 2A-B are photographs showing a side view of the vessel containingthe mixture of Example 4 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 2A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 2B), also after 60 min ofstirring.

FIGS. 3A-B are photographs showing a side view of the vessel containingthe mixture of Example 5 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 3A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 3B), also after 60 min ofstirring.

FIGS. 4A-B are photographs showing a side view of the vessel containingthe mixture of Example 6 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 4A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 4B), also after 60 min ofstirring.

FIGS. 5A-B are photographs showing a side view of the vessel containingthe mixture of Example 7 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 5A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 5B), also after 60 min ofstirring.

FIGS. 6A-B are photographs showing a side view of the vessel containingthe mixture of Example 8 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 6A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 6B), also after 60 min ofstirring.

FIGS. 7A-B are photographs showing a side view of the vessel containingthe mixture of Example 9 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 7A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 7B), also after 60 min ofstirring.

FIGS. 8A-B are photographs showing a side view of the vessel containingthe mixture of Example 10 after 60 min of stirring then briefly allowingthe mixture to settle (FIG. 8A), and a top view of the inside of thevessel after decanting the supernatant (FIG. 8B), also after 60 min ofstirring.

FIGS. 9 and 10 are photographs showing a top-down (FIG. 9) and side(FIG. 10) view of the contents in the beaker in Example 13 beforestirring.

FIG. 11 is a photograph showing the contents of the beaker in Example 13after stirring for 4 min, then allowing most of the solids to settle.FIG. 11 shows stringers of oil separating from the oil sand.

FIG. 12 is a photograph showing the contents of the beaker in Example 13after stirring for 10 minutes. FIG. 12 shows stringers of oil separatingfrom the oil sand.

FIG. 13 is a photograph showing the contents of the beaker in Example13, showing that sand free of oil that had settled to the bottom of thebeaker a few minutes after stirring was stopped.

FIG. 14 is a photograph showing the contents of the beaker in Example13, showing that agglomerating oil deposits sat on top of the sand afterdecanting the solution into another beaker.

FIGS. 15-16 are photographs showing the contents of the beaker ofExample 13 after stirring 30 min, then decanting the solution intoanother beaker. FIG. 15 is a photograph of “free” oil sticking to theglass of the beaker in which the oil sand and extractant were stirred,after decanting the extractant liquid comprising some extracted oil intoa second beaker. FIG. 16 is a photograph showing the remaining sand andoil in the beaker in which the oil sand and extractant were stirredafter decanting the extractant liquid comprising some extracted oil intothe second beaker.

FIG. 17 is a photograph showing the sand, oil and magnetic stir barremaining in the beaker of Example 13 after stirring for 1 hour anddecanting the resultant supernatant.

FIG. 18 is a photograph showing the oil remaining on the glass of thefirst beaker of Example 13 after transferring the sand, oil andextractant to a second beaker.

FIG. 19 is a chart showing the size distribution of the solids in theAthabasca oil sands of Example 14.

FIG. 20 depicts a series of photographs showing the contents of thebeakers in Example 17, illustrating the effects of adding a solutioncomprising 5 parts of the composition of Example 1 and 95 parts water byweight to light tar oil in a glass beaker with subsequent stirring, andthe effect of adding water to light tar oil in a glass beaker withsubsequent stirring.

FIG. 21 depicts a series of photographs showing the contents of thebeakers in Example 18, illustrating the effects of adding a solutioncomprising 5 parts of the composition of Example 1 and 95 parts water byweight to coal tar in a glass beaker with subsequent stirring, and theeffect of adding water to coal tar in a glass beaker with subsequentstirring.

FIG. 22 depicts series of photographs showing the contents of thebeakers in Example 19, illustrating showing the effects of adding asolution comprising 5 parts of the composition of Example 1 and 95 partswater by weight to oil-contaminated sludge in a glass beaker withsubsequent stirring, and the effect of adding water to oil-contaminatedsludge in a glass beaker with subsequent stirring.

FIG. 23 is a process flow diagram illustrating the process described inExample 21 for frothing and extracting oil from Athabasca oils sand andquantifying recovery of oil therefrom, to quantitatively asses thefoaming properties of Compositions of the Invention.

FIG. 24 depicts three photographs illustrating aeration experimentsperformed as described in Example 21, but without recovery andquantification of oil, to qualitatively asses the foaming properties ofillustrative Compositions of the Invention.

FIG. 25 depicts two photographs illustrating the results of when coaltar coated sand is stirred with a solution comprising 5 parts of thecomposition of Example 1 and 95 parts water by weight for two hours,then aerated as described in Example 21.

FIG. 26 depicts a series of photographs showing the effect of reducingthe pH of a solution comprising 5 parts of the composition of Example 1and 95 parts water by weight on suspended fines after extraction andremoval of extracted oil from a 5 g sample of Athabasca oil sand in theexperiment described in Example 23.

DETAILED DESCRIPTION

The word ‘about’ when immediately preceding a numerical value means arange of plus or minus 10% of that value, e.g., “about 50” means 45 to55, “about 25,000” means 22,500 to 27,500, etc. Furthermore, the phrases“less than about” a value or “greater than about” a value should beunderstood in view of the definition of the term “about” providedherein.

Compositions of the Invention Aqueous Compositions

In a first aspect, the present invention aqueous compositions comprisingabout 1 wt % to about 50 wt % of plant material, 0 to about 20 wt % of apolysaccharide, 0% to about 10 wt % of an alcohol, 0% to about 15 wt %of a base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of anacid, 0% to about 10 wt % of an additive, and about 10 wt % to about 95wt % of water. In some embodiments, the plant material comprises a plantprotein.

In other embodiments, the aqueous compositions comprise from about 1 toabout 30 wt % of plant material and 0 to about 10 wt % of apolysaccharide. In certain embodiments, the aqueous compositionscomprise from about 1 to about 10 wt % of plant material and 0 to about5 wt % of a polysaccharide. In still other embodiments, the aqueouscompositions comprise from about 1 to about 5 wt % of plant material and0 to about 1 wt % of a polysaccharide. In some embodiments, the aqueouscompositions do not comprise a polysaccharide other than that present inor derived from the plant material. In other embodiments, the aqueouscompositions do not comprise a polysaccharide.

Polysaccharides which are useful in the present aqueous composition aretypically water-soluble, e.g., soluble in water or water-alcoholsolutions. In general, the polysaccharides are plant-derivedpolysaccharides, including related materials such as pectins. Examplesof polysaccharides that are useful for the present aqueous compositionsinclude, but are not limited to, water-soluble cellulose derivatives,seaweed polysaccharides such as alginate and carrageenan, seedmucilaginous polysaccharides, complex plant exudate polysaccharides suchas gum arabic, tragacanth, guar gum, pectin, ghatti gum and the like,and microbially synthesized polysaccharides such as xanthan gum, ormixtures of such polysaccharides. In certain embodiments, thepolysaccharide is guar gum, pectin, gum arabic and mixtures thereof. Insome embodiments, the polysaccharide is a synthetic polysaccharide suchas synthetic guar. In one embodiment, the polysaccharide is guar gum. Insome embodiments, the present aqueous compositions do not comprise oneor more of the aforementioned polysaccharides other than that present inor derived from the plant material. In other embodiments, the presentaqueous compositions do not comprise one or more of the aforementionedpolysaccharides.

The polysaccharide can be present in the aqueous compositions in anamount ranging from 0 to about 20 wt % (e.g., 0 to about 0.5 wt %, about0.5 wt % to about 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % toabout 3 wt %, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt%, about 5 wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7wt % to about 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % toabout 10 wt %, about 10 wt % to about 11 wt %, about 11 wt % to about 12wt %, about 12 wt % to about 13 wt %, about 13 wt % to about 14 wt %,about 14 wt % to about 15 wt %, about 15 wt % to about 16 wt %, about 16wt % about 17 wt %, about 17 wt % to about 18 wt %, about 18 wt % toabout 19 wt %, about 19 wt % to about 20 wt %, or any other value orrange of values therein). In some embodiments, the polysaccharide ispresent in an amount of from about 0.1 wt % to about 5 wt %. In otherembodiments, the present aqueous compositions do not comprise apolysaccharide (i.e., 0 wt %).

Similarly, plant material useful in the present aqueous compositions canbe those from any plant. The plant material can include any part of theplant, e.g., trunk, stems, seeds, roots, leaves, branches, bark,flowers, nuts, sprouts, or any other part of a plant. In someembodiments, the plant material comprises plant protein. In someembodiments, the plant proteins are prolamines. In certain embodiments,the plant is a cereal plant. Suitable cereal plants include, but are notlimited to, corn, rice, wheat, barley, sorghum, millet, rye, triticale,fonio, buckwheat, spelt, quinoa, flax, or mixtures thereof. In otherembodiments, the plant material is lentils (e.g., green, yellow, black),soy beans, hemp seed, chia, grass, wheat grass and barley (e.g., pearl,groat). In some embodiments, the plant is cotton, and the plant materialis cotton seeds. In some embodiments, the plant is flax, and the plantmaterial is flax seeds. In some embodiments, the plant is wheat, and theplant material is wheat germ. In some embodiments, the plant material iscorn gluten meal. In still other embodiments, the corn gluten mealcomprises a protein, and the protein is gluten. In other embodiments,the gluten is corn gluten.

In some embodiments, the plant material has a protein content of fromabout 5 wt % to about 100 wt % (e.g., 5 to about 10 wt %, about 10 wt %to about 15 wt %, about 15 wt % to about 20 wt %, about 20 wt % to about25 wt %, about 25 wt % to about 30 wt %, about 30 wt % to about 35 wt %,about 35 wt % to about 40 wt %, about 40 wt % to about 45 wt %, about 45wt % to about 50 wt %, about 50 wt % to about 55 wt %, about 55 wt % toabout 60 wt %, about 60 wt % to about 65 wt %, about 65 wt % to about 70wt %, about 70 wt % to about 75 wt %, about 75 wt % to about 80 wt %,about 80 wt % to about 85 wt %, about 85 wt % to about 90 wt %, about 90wt % about 95 wt %, about 95 wt % to about 100 wt %, or any other valueor range of values therein) of the plant material.

In some embodiments, the present aqueous compositions comprise a plantprotein as measured by Biuret assay (as described hereinbelow), in anamount ranging from about 0.1 ppt (part per thousand) to about 100 ppt(e.g., from about 0.1 ppt to about 0.2 ppt, from about 0.2 ppt to about0.3 ppt, from about 0.3 ppt to about 0.4 ppt, from about 0.4 ppt toabout 0.5 ppt, from about 0.5 ppt to about 0.6 ppt, from about 0.6 pptto about 0.7 ppt, from about 0.7 ppt to about 0.8 ppt, from about 0.8ppt to about 0.9 ppt, from about 0.9 ppt to about 1.0 ppt, from about 1ppt to about 5 ppt, from about 5 ppt to about 10 ppt, from about 10 pptto about 15 ppt, from about 15 ppt to about 20 ppt, from about 20 ppt toabout 25 ppt, from about 25 ppt to about 30 ppt, from about 30 ppt toabout 35 ppt, from about 35 ppt to about 40 ppt, from about 40 ppt toabout 45 ppt, from about 45 ppt to about 50 ppt, from about 50 ppt toabout 55 ppt, from about 55 ppt to about 60 ppt, from about 60 ppt toabout 65 ppt, from about 65 ppt to about 70 ppt, from about 70 ppt toabout 75 ppt, from about 75 ppt to about 80 ppt, from about 80 ppt toabout 85 ppt, from about 85 ppt to about 90 ppt, from about 90 ppt toabout 95 ppt, from about 95 ppt to about 100 ppt, or any other value orrange of values therein) of the aqueous composition.

Prolamine is a cereal-derived protein that is typically soluble indilute aqueous alcohol solutions. Examples of suitable prolamines thatare useful in the present aqueous compositions include, but are notlimited to, corn-derived prolamine (also referred to as zein),barley-derived prolamine or hordein, wheat-derived prolamine or gliadin,or corn gluten. Zein is extractable from corn or maize.

Zein can be extracted from corn gluten by physical separation means orchemical separation means. In one embodiment, the zein has a molecularweight of about 20,000 to about 35,000 Da. In another embodiment, thezein has a molecular weight of from about 19,000 Da to about 22,000 Da.

In certain embodiments, the plant protein is separated from plantmaterial. For example, the plant material can be combined with a solventor solvent blend to extract plant protein from the plant material. Incertain embodiments, the plant material can be combined with a solventor solvent blend to separate the plant protein from the plant material.Suitable solvents can include water, or an organic solvent, in theabsence or presence of water. Suitable organic solvents include, but arenot limited to, C₁ to C₃ alcohols such as methanol, ethanol, n-propanoland i-propanol; glycols such as ethylene glycol, propylene glycol,polyethylene glycol; glycol ethers; amine solvents such as butylamine;aminoalcohols such as ethanolamine, diethanolamine, diisopropanolamine;ketone-containing solvents such as acetone, acetic acid and acetamide;aromatic alcohols such as benzyl alcohol; and mixtures thereof.

In other embodiments, the plant material can be combined with a solventor solvent blend and then can be treated with acid or base to separateplant protein from the plant material. Suitable acids and bases forseparation of plant protein from plant material are those as describedherein which are useful in a preparing a Composition of the Invention.In some embodiments, the pH of the mixture of the plant material andsolvent may be adjusted to from about 2 to about 14 (e.g., from about 2to about 3, from about 3 to about 4, from about 4 to about 5, from about5 to about 6, from about 6 to about 7, from about 7 to about 8, fromabout 8 to about 9, from about 9 to about 10, from about 10 to about 11,from about 11 to about 12, from about 12 to about 13, from about 13 toabout 14, or any other value or range of values therein). The mixture ofthe plant material and solvent, which can further comprise an acid orbase, may be agitated (e.g., stirring, mixing).

In some embodiments, the plant material or plant protein may reduced insize prior to use in the present aqueous compositions. For example, theplant material or plant protein may be ground, chopped, pulverized,milled or macerated to reduce the size of the plant material, to enablethe dissolution, suspension or admixture of the plant material orprotein in the present aqueous compositions. For example, the plantmaterial or plant protein may be ground, chopped or macerated to provideparticulate sizes (e.g., length, width or average diameter) ranging fromabout 0.1 mm to about 1 cm (e.g., from about 0.1 mm to about 0.2 mm,from about 0.2 mm to about 0.3 mm, from about 0.3 mm to about 0.4 mm,from about 0.4 mm to about 0.5 mm, from about 0.5 mm to about 0.6 mm,from about 0.6 mm to about 0.7 mm, from about 0.7 mm to about 0.8 mm,from about 0.8 mm to about 0.9 mm, from about 0.9 mm to about 1 mm, fromabout 1 mm to about 2 mm, from about 2 mm to about 3 mm, from about 3 mmto about 4 mm, from about 4 mm to about 5 mm, from about 5 mm to about 6mm, from about 6 mm to about 7 mm, from about 7 mm to about 8 mm, fromabout 8 mm to about 9 mm, from about 9 mm to about 1 cm, or any othervalue or range of values therein).

The mixture comprising the plant material can be admixed, optionallywith agitation, for a period of about 10 minutes, about 20 minutes,about 30 minutes, about 40 minutes, about 50 minutes, about 1 hour,about 2 hours, about 3 hours, about 4 hours, or any other value or rangeof values therein or thereabove) and at a temperature of from about 5°C. to about 100° C. (e.g., about 5° C. to about 10° C., about 10° C. toabout 15° C., about 15° C. to about 20° C., about 20° C. to about 25°C., about 25° C. to about 30° C., about 30° C. to about 35° C., about35° C. to about 40° C., about 40° C. to about 45° C., about 45° C. toabout 50° C., about 50° C. to about 55° C., about 55° C. to about 60°C., about 60° C. to about 65° C., about 65° C. to about 70° C., about70° C. to about 75° C., about 75° C. to about 80° C., about 80° C. toabout 85° C., about 85° C. to about 90° C., about 90° C. to about 95°C., about 95° C. to about 100° C., or any other value or range of valuestherein). The solvent and pH can be selected to suspend or solubilizeprotein present in the plant material. The remaining components (e.g.,cellulosic material) from the plant material can precipitate out ofsolution, and the plant protein can then be separated by decanting thesupernatant or by filtration.

In other embodiments, the plant protein may be obtained as apre-separated material. For example, zein extracted from corn may beobtained commercially from, e.g., Chemieliva Pharmaceutical Co., Ltd.,HBC Chem. Inc., Matrix Marketing GMBH, and Spectrum Chemical Mfg. Corp.

In some embodiments, the plant material is present in the aqueouscompositions in an amount ranging from about 1 to 50 wt % (e.g., about 1to about 2 wt %, about 2 wt % to about 3 wt %, about 3 wt % to about 4wt %, about 4 wt % to about 5 wt %, about 5 wt % to about 6 wt %, about6 wt % to about 7 wt %, about 7 wt % to about 8 wt %, about 8 wt % toabout 9 wt %, about 9 wt % to about 10 wt %, about 10 wt % to about 11wt %, about 11 wt % to about 12 wt %, about 12 wt % to about 13 wt %,about 13 wt % to about 14 wt %, about 14 wt % to about 15 wt %, about 15wt % to about 20 wt %, about 20 wt % to about 25 wt %, about 25 wt % toabout 30 wt %, about 30 wt % to about 35 wt %, about 35 wt % to about 40wt %, about 40 wt % to about 45 wt %, about 45 wt % to about 50 wt %, orany other value or range of values therein) of the aqueous composition.In some embodiments, the plant material is present in an amount of fromabout 1 wt % to about 30 wt %. In certain embodiments, the plantmaterial is present in an amount of from about 1 wt % to about 10 wt %.In other embodiments, the plant material is present in an amount of fromabout 1 wt % to about 5 wt %.

The present aqueous compositions can further comprise an acid or a base.The acid or base is useful for adjusting the pH of the aqueouscompositions. For example, the acid or base is useful for adjusting thepH of the present aqueous compositions to a pH of about 1 to about 14(e.g., from about 1 to about 2, from about 2 to about 2, from about 3 toabout 4, from about 4 to about 5, from about 5 to about 6, from about 6to about 7, from about 7 to about 8, from about 8 to about 9, from about9 to about 10, from about 10 to about 11, from about 11 to about 12,from about 12 to about 13, from about 13 to about 14, or any other valueor range of values therein). In certain embodiments, the pH of thepresent aqueous composition ranges from about 3.5 to about 13; in otherembodiments, from about 6.5 to about 8.5. In some embodiments, the pH isabout 13; in other embodiments, the pH is about 7.5 to about 8.4. Incertain embodiments, the pH of the present aqueous composition rangesfrom about 5 to about 13; from about 6 to about 13; from about 7 toabout 13; from about 8 to about 13; from about 9 to about 13; from about10 to about 13; from about 11 to about 13; from about 12 to about 13.

Such pH adjustment can improve the dispersibility of the protein orpolysaccharide, if present, of the present aqueous compositions. Acidsuseful in the present aqueous compositions include inorganic acids suchas carbonic acid, sulfuric acid, or hydrochloric acid. Organic acids canalternatively be employed. Suitable organic acids include C₁ to C₂₀organic acids such as formic acid, citric acid, malic acid, adipic acid,tannic acid, lactic acid, ascorbic acid, acetic acid, fumaric acid, andmixtures thereof. In one embodiment, the acid is citric acid.

The acid can be present in the aqueous compositions in an amount from 0wt % to about 10 wt % (e.g., 0 to about 0.5 wt %, about 0.5 wt % toabout 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 3 wt%, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt %, about 5wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7 wt % toabout 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % to about 10 wt%, or any other value or range of values therein) of the aqueouscomposition. In some embodiments, the acid is present from about 0.01 wt% to about 2 wt % of the aqueous compositions. In one embodiment, theacid is present in about 0.03 wt %. In some embodiments, the aqueouscompositions do not comprise an acid.

The present aqueous composition can comprise a base. Bases useful in thepresent aqueous compositions are organic or inorganic bases. Suitableinorganic bases include alkali metal or alkaline earth metal compoundssuch as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, magnesium carbonate and calcium carbonate. Other suitablebases include ammonium hydroxide, substituted amine bases and ammonia.

The base can present in the aqueous compositions in an amount from 0 wt% to about 15 wt % (e.g., 0 to about 0.5 wt %, about 0.5 wt % to about 1wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 3 wt %, about3 wt % to about 4 wt %, about 4 wt % to about 5 wt %, about 5 wt % toabout 6 wt %, about 6 wt % to about 7 wt %, about 7 wt % to about 8 wt%, about 8 wt % to about 9 wt %, about 9 wt % to about 10 wt %, about 10wt % to about 11 wt %, about 11 wt % to about 12 wt %, about 12 wt % toabout 13 wt %, about 13 wt % to about 14 wt %, about 14 wt % to about 15wt %, or any other value or range of values therein). In someembodiments, the base is present from about 1 wt % to about 15 wt % ofthe aqueous compositions. In one embodiment, the base is present inabout 7 wt %. In some embodiments, the aqueous compositions do notcomprise a base.

The present aqueous compositions can also comprise a salt. Salts usefulin the present aqueous compositions include organic or inorganic salts.Suitable salts include alkali or alkaline earth metal salts such assodium chloride, potassium chloride, calcium chloride, magnesiumchloride, ammonium chloride, sodium bromide, potassium bromide, calciumbromide, magnesium bromide, ammonium bromide, sodium iodide, potassiumiodide, calcium iodide, magnesium iodide, ammonium iodide, sodiumsulfate, potassium sulfate, calcium sulfate, magnesium sulfate, ammoniumsulfate.

The salt can present in the aqueous compositions in an amount from 0 wt% to about 10 wt % (e.g., 0 to about 0.5 wt %, about 0.5 wt % to about 1wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 3 wt %, about3 wt % to about 4 wt %, about 4 wt % to about 5 wt %, about 5 wt % toabout 6 wt %, about 6 wt % to about 7 wt %, about 7 wt % to about 8 wt%, about 8 wt % to about 9 wt %, about 9 wt % to about 10 wt %, or anyother value or range of values therein) of the aqueous composition. Insome embodiments, the salt is present from about 0.01 wt % to about 0.05wt % of the aqueous compositions. In some embodiments, the aqueouscompositions do not comprise a salt.

The present aqueous compositions comprise water. The amount of water inthe present aqueous compositions can range from about 10 to about 90 wt% (e.g., about 10 wt % to about 15 wt %, about 15 wt % to about 20 wt %,about 20 wt % to about 25 wt %, about 25 wt % to about 30 wt %, about 30wt % to about 35 wt %, about 35 wt % to about 40 wt %, about 40 wt % toabout 45 wt %, about 45 wt % to about 50 wt %, about 50 wt % to about 55wt %, about 55 wt % to about 60 wt %, about 60 wt % to about 65 wt %,about 65 wt % to about 70 wt %, about 70 wt % to about 75 wt %, about 75wt % to about 80 wt %, about 80 wt % to about 85 wt %, about 85 wt % toabout 90 wt %, or any other value or range of values therein). Incertain embodiments, the aqueous compositions comprise from about 80 wt% to about 90 wt % water. In one embodiment, the aqueous compositionscomprise about 69 wt % water.

The present aqueous compositions can further comprise an organicsolvent, in the absence or presence of water. Suitable organic solventsinclude, but are not limited to, C₁ to C₃ alcohols such as methanol,ethanol, n-propanol and i-propanol. Alternatively glycols such asethylene glycol, propylene glycol and polyethylene glycol, andketone-containing solvents such as acetone can be employed. In certainembodiments, the aqueous organic solvent is ethanol or i-propanol. Inone embodiment, the aqueous compositions comprise water and an alcohol;in another embodiment, water and ethanol or i-propanol.

The amount of organic solvent, if present, can be selected based onfactors such as its miscibility in water, if present, and the amount ofprotein. The organic solvent can be present in the aqueous compositionsin an amount ranging from 0 wt % to about 10 wt % (e.g., 0 wt % to about1 wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 3 wt %,about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt %, about 5 wt %to about 6 wt %, about 6 wt % to about 7 wt %, about 7 wt % to about 8wt %, about 8 wt % to about 9 wt %, about 9 wt % to about 10 wt %, orany other value or range of values therein) of the aqueous composition.In certain embodiments, the organic solvent is present in an amount ofabout 2.5 wt %. In some embodiments, the aqueous compositions do notcomprise an organic solvent.

The present aqueous compositions can also comprise one or more otheradditives. Suitable additives include, but are not limited to,detergents, as surface tension modifiers, flocculants, dispersants,rheology modifiers and emulsifiers. Illustrative additives arepolysorbates, oils (e.g., canola oil, vegetable oils, etc.) In someembodiments, the present aqueous compositions comprise lime (e.g., quicklime, slaked lime, Ca(OH)₂, Type-S hydrated lime). In certainembodiments, the lime is Type-S hydrated lime. The additive(s) can bepresent in the aqueous compositions in amounts ranging from 0 to about10% (e.g., 0 to about 0.5 wt %, about 0.5 wt % to about 1 wt %, about 1wt % to about 2 wt %, about 2 wt % to about 3 wt %, about 3 wt % toabout 4 wt %, about 4 wt % to about 5 wt %, about 5 wt % to about 6 wt%, about 6 wt % to about 7 wt %, about 7 wt % to about 8 wt %, about 8wt % to about 9 wt %, about 9 wt % to about 10 wt %, or any other valueor range of values therein) of the aqueous composition. In certainembodiments, the additive is Type-S hydrated lime and is present in anamount of about 0.5 wt %. In some embodiments, the aqueous compositionsdo not comprise an additive. In some embodiments, the aqueouscompositions do not comprise lime. In some embodiments, the aqueouscompositions do not comprise S type hydrated lime.

In particular embodiments of the present invention, the aqueouscompositions comprise a polysaccharide that is guar gum and plantmaterial that is corn gluten meal. In other embodiments, the aqueouscompositions further comprise one or more of water, isopropanol, citricacid, Type S hydrated lime, sodium hydroxide, and sodium chloride. Inother embodiments of the present invention, the aqueous compositionscomprise plant material that is corn gluten meal, and do not contain apolysaccharide other than that present in or derived from the corngluten meal. In other embodiments, the aqueous compositions furthercomprise one or more of water, isopropanol, citric acid, Type S hydratedlime, sodium hydroxide, and sodium chloride.

Thus, in one embodiment, the present invention provides an aqueouscomposition comprising about 1 wt % to about 50 wt % of plant material,0 to about 20 wt % of a polysaccharide, 0% to about 10 wt % of analcohol, 0% to about 15 wt % of a base, 0% to about 10 wt % of a salt,0% to about 10 wt % of an acid, 0% to about 10 wt % of an additive, andabout 10 wt % to about 95 wt % of water, wherein the aqueous compositionhas a pH of from about 9 to about 13.

In one embodiment, the aqueous composition comprises from about 1 wt %to about 30 wt % of the plant material and 0 to about 10 wt % of thepolysaccharide. In certain embodiments, the aqueous compositioncomprises from about 1 wt % to about 10 wt % of the plant material and 0to about 5 wt % of the polysaccharide. In other embodiments, the aqueouscomposition comprises from about 1 wt % to about 5 wt % of the plantmaterial and 0 to about 1 wt % of the polysaccharide. In someembodiments, the plant a cereal. In some embodiments, the cereal iscorn, rice, wheat, barley, sorghum, millet, rye, triticale, fonio, flax,buckwheat, spelt or quinoa. In one embodiment, the cereal is corn. Inother embodiments, the plant material is lentils (e.g., green, yellow,black), soy beans, hemp seed, chia, grass, wheat grass and barley (e.g.,pearl, groat). In some embodiments, the plant material comprises a plantprotein. In some embodiments, the plant protein is from corn glutenmeal. In other embodiments, the plant is cotton. In certain embodiments,the plant protein is prolamine, zein, hordein, or gliadin. In someembodiments, the polysaccharide of the present aqueous composition isalginate, carrageenan, gum Arabic, tragacanth gum, guar gum, pectin,ghatti gum, xanthan gum, or mixtures thereof. In some embodiments, thepolysaccharide is about 0.5 wt % to about 2 wt % of the aqueouscomposition. In some embodiments, the aqueous compositions do notcomprise any of the aforementioned polysaccharides other than thosepresent in or derived from the plant material. In other embodiments, theaqueous compositions do not comprise any of the aforementionedpolysaccharides. In other embodiments, the aqueous compositions do notcomprise polysaccharide.

In some embodiments, the aqueous composition further comprises analcohol. In certain embodiments, the alcohol is ethanol, methanol, orisopropanol. In one embodiment, the alcohol is isopropanol. In someembodiments, the alcohol is about 0 wt % to about 10 wt % of the aqueouscomposition. In some embodiments, the aqueous composition does notcomprise an alcohol. In some embodiments, the aqueous compositionfurther comprises a base. In certain embodiments, the base is aninorganic base or an inorganic base. In other embodiments, the inorganicbase is an alkali metal or alkaline earth metal base. In someembodiments, the inorganic base is sodium hydroxide, lithium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate, sodiumbicarbonate, potassium bicarbonate, magnesium carbonate or calciumcarbonate. In certain embodiments, the base is about 0 wt % to about 10wt % of the aqueous composition. In some embodiments, the aqueouscomposition does not comprise a base.

In some embodiments, the aqueous composition further comprises a salt.In certain embodiments, the salt is sodium chloride, potassium chloride,calcium chloride, magnesium chloride, ammonium chloride, sodium bromide,potassium bromide, calcium bromide, magnesium bromide, ammonium bromide,sodium iodide, potassium iodide, calcium iodide, magnesium iodide,ammonium iodide, sodium sulfate, potassium sulfate, calcium sulfate,magnesium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate,magnesium nitrate, calcium nitrate, ammonium nitrate or mixturesthereof. In certain embodiments, the salt is about 0 wt % to about 10 wt% of the aqueous composition. In some embodiments, the aqueouscomposition does not comprise a salt.

In some embodiments, the aqueous composition further comprises an acid.In certain embodiments, the acid is an organic acid. In otherembodiments, the acids include inorganic acids. In certain embodiments,the inorganic acids include carbonic acid, sulfuric acid, orhydrochloric acid. In some embodiments, the acid is a C1-C20 organicacid. In certain embodiments, the acid is citric acid, formic acid,ascorbic acid, acetic acid, malic acid, adipic acid, tannic acid, lacticacid, fumaric acid, or mixtures thereof. In one embodiment, the acid iscitric acid. In certain embodiments, the acid is about 0 wt % to about10 wt % of the aqueous composition. In some embodiments, the aqueouscomposition does not comprise an acid.

In some embodiments, the aqueous composition of further comprises anadditive. In certain embodiments, the additive is lime. In oneembodiment, the lime is Type S Hydrated certain embodiments, theadditive is lime. In certain embodiments, the lime is Type S HydratedLime. In certain embodiments, the Type S Hydrated Lime is about 0 wt %to about 10 wt % of the aqueous composition. In some embodiments, theaqueous composition does not comprise an additive. In some embodiments,the aqueous composition does not comprise lime.

In some embodiments, the aqueous composition comprises about 10 wt % toabout 90 wt % water. In certain embodiments, the aqueous compositioncomprises about 80 wt % to about 90 wt % water. In certain embodiments,the aqueous composition comprises a polysaccharide and thepolysaccharide and plant protein are in the form of a complex. Incertain embodiments, the pH of the aqueous composition is from about 6to about 8. In certain embodiments, the aqueous composition does notcomprise a polysaccharide other than that derived from the plantmaterial, wherein the plant material is corn gluten meal, and whereinthe aqueous composition optionally further comprises one or more ofisopropanol, citric acid, Type S hydrated lime, sodium hydroxide, andsodium chloride. In one embodiment, the aqueous compositions furthercomprise a substrate.

Preparation of the Aqueous Compositions

The present aqueous compositions can be prepared by admixing the aqueouscompositions' components, optionally in the presence of water or anorganic solvent. For example, the aqueous compositions can be preparedby admixing the plant material component, in an amount as describedhereinabove, with one or both of water and an organic solvent to form aplant material mixture. The plant material mixture can be a suspensionor solution and can further comprise an acid or base. The plant materialcan be added to the water, the organic solvent or both, or vice versa.The plant material mixture can be stirred or agitated until the plantmaterial is suspended or substantially dissolved (e.g., about 10minutes, about 20 minutes, about 30 minutes, about 40 minutes, about 50minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, orany other value or range of values therein or thereabove). The plantmaterial mixture can be heated at a temperature of from about 5° C. toabout 100° C. (e.g., about 5° C. to about 10° C., about 10° C. to about15° C., about 15° C. to about 20° C., about 20° C. to about 25° C.,about 25° C. to about 30° C., about 30° C. to about 35° C., about 35° C.to about 40° C., about 40° C. to about 45° C., about 45° C. to about 50°C., about 50° C. to about 55° C., about 55° C. to about 60° C., about60° C. to about 65° C., about 65° C. to about 70° C., about 70° C. toabout 75° C., about 75° C. to about 80° C., about 80° C. to about 85°C., about 85° C. to about 90° C., about 90° C. to about 95° C., about95° C. to about 100° C., or any other value or range of values therein),optionally with mixing. In certain embodiments, the plant materialmixture is prepared at ambient temperature (e.g., about 23° C.).

In some embodiments, the plant material is wetted with water (e.g.,contacted or admixed with water, soaked in water, saturated with water)prior to admixing with other ingredients to form the present aqueouscompositions. For example, the plant material may wetted with water fora time period ranging from about 5 minutes to about 168 hours (e.g.,from about 5 minutes to about 10 minutes, from about 10 minutes to about20 minutes, from about 20 minutes to about 30 minutes, from about 30minutes to about 40 minutes, from about 40 minutes to about 50 minutes,from about 50 minutes to about 1 hour, from about 1 hour to about 2hours, from about 2 hours to about 3 hours, from about 3 hours to about4 hours, from about 4 hours to about 5 hours, from about 5 hours toabout 6 hours, from about 6 hours to about 7 hours, from about 7 hoursto about 8 hours, from about 8 hours to about 9 hours, from about 9hours to about 10 hours, from about 10 hours to about 11 hours, fromabout 11 hours to about 12 hours, from about 12 hours to about 14 hours,from about 14 hours to about 16 hours, from about 16 hours to about 18hours, from about 18 hours to about 20 hours, from about 20 hours toabout 22 hours, from about 22 hours to about 24 hours, from about 24hours to about 28 hours, from about 28 hours to about 32 hours, fromabout 32 hours to about 36 hours, from about 36 hours to about 40 hours,from about 40 hours to about 44 hours, from about 44 hours to about 48hours, from about 48 hours to about 72 hours, from about 72 hours toabout 96 hours, from about 96 hours to about 120 hours, from about 120hours to about 144 hours, from about 144 hours to about 168 hours, orany other value or range of values therein). In some embodiments, thewetted plant material may be admixed with the water employed forwetting. In some embodiments, the plant material is wetted in a sterileenvironment. In other embodiments, the plant material which has beenwetted with water may be separated from the wetting water (e.g., whenthe plant material has been immersed in water to effect said wetting)by, e.g., decantation or filtration, prior to admixing the protein withadditional components of the present aqueous compositions. In someembodiments, the plant material is not wetted.

In other embodiments, an acid or a base is added to water, organicsolvent or both, and the resultant solution is added to the plantmaterial mixture, or vice versa. The acid or base can be undiluted orpresent as a mixture with water or an organic solvent. After addition ofthe acid or base, in certain embodiments the plant material mixture isallowed to stand for a period of time prior to addition of othercomponents. For example, the plant material mixture can be allowed tostand for a period of about 10 minutes, about 20 minutes, about 30minutes, about 40 minutes, about 50 minutes, about 1 hour, about 2hours, about 3 hours, about 4 hours, about 8 hours, or any other valueor range of values therein or thereabove). The plant material mixturecan be allowed to stand at a temperature of from about 5° C. to about100° C. (e.g., about 5° C. to about 10° C., about 10° C. to about 15°C., about 15° C. to about 20° C., about 20° C. to about 25° C., about25° C. to about 30° C., about 30° C. to about 35° C., about 35° C. toabout 40° C., about 40° C. to about 45° C., about 45° C. to about 50°C., about 50° C. to about 55° C., about 55° C. to about 60° C., about60° C. to about 65° C., about 65° C. to about 70° C., about 70° C. toabout 75° C., about 75° C. to about 80° C., about 80° C. to about 85°C., about 85° C. to about 90° C., about 90° C. to about 95° C., about95° C. to about 100° C., or any other value or range of values therein).In certain embodiments, after addition of the acid or base, the plantmaterial mixture is allowed to stand at ambient temperature (e.g., about23° C.).

Where the aqueous compositions comprise a polysaccharide other than thatwhich is present or derived from the plant material, the polysaccharideis added to the plant material mixture, or vice versa. In someembodiments, protein from the plant material and polysaccharide form aprotein-polysaccharide complex in solution. Typically the plant materialand polysaccharide are admixed with agitation (e.g., stirring, mixing).The mixture comprising the plant material and polysaccharide can beadmixed with agitation for a period of about 10 minutes, about 20minutes, about 30 minutes, about 40 minutes, about 50 minutes, about 1hour, about 2 hours, about 3 hours, about 4 hours, or any other value orrange of values therein or thereabove) and at a temperature of fromabout 5° C. to about 100° C. (e.g., about 5° C. to about 10° C., about10° C. to about 15° C., about 15° C. to about 20° C., about 20° C. toabout 25° C., about 25° C. to about 30° C., about 30° C. to about 35°C., about 35° C. to about 40° C., about 40° C. to about 45° C., about45° C. to about 50° C., about 50° C. to about 55° C., about 55° C. toabout 60° C., about 60° C. to about 65° C., about 65° C. to about 70°C., about 70° C. to about 75° C., about 75° C. to about 80° C., about80° C. to about 85° C., about 85° C. to about 90° C., about 90° C. toabout 95° C., about 95° C. to about 100° C., or any other value or rangeof values therein). In certain embodiments, the mixture comprising theplant material and polysaccharide is agitated at ambient temperature(e.g., about 23° C.).

In some embodiments, a salt is added to the plant material mixture, orvice versa, typically with agitation (e.g., stirring, mixing). The plantmaterial mixture can be agitated for a period of about 10 minutes, about20 minutes, about 30 minutes, about 40 minutes, about 50 minutes, about1 hour, about 2 hours, about 3 hours, about 4 hours, or any other valueor range of values therein or thereabove) and at a temperature of fromabout 5° C. to about 100° C. (e.g., about 5° C. to about 10° C., about10° C. to about 15° C., about 15° C. to about 20° C., about 20° C. toabout 25° C., about 25° C. to about 30° C., about 30° C. to about 35°C., about 35° C. to about 40° C., about 40° C. to about 45° C., about45° C. to about 50° C., about 50° C. to about 55° C., about 55° C. toabout 60° C., about 60° C. to about 65° C., about 65° C. to about 70°C., about 70° C. to about 75° C., about 75° C. to about 80° C., about80° C. to about 85° C., about 85° C. to about 90° C., about 90° C. toabout 95° C., about 95° C. to about 100° C., or any other value or rangeof values therein). In certain embodiments, the plant material mixtureis agitated at ambient temperature (e.g., about 23° C.).

The plant material mixture can then be admixed with one or moreadditives described above. The plant material mixture can be added tothe one or more additives, or vice versa. Typically the plant materialmixture and one or more additives are admixed with agitation (e.g.,stirring, mixing). The resultant mixture can be agitated for a period oftime until it becomes uniform, e.g., a solution or a uniform suspension.For example, the resultant mixture can be agitated for a period of about10 minutes, about 20 minutes, about 30 minutes, about 40 minutes, about50 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours,or any other value or range of values therein or thereabove) and at atemperature of from about 5° C. to about 100° C. (e.g., about 5° C. toabout 10° C., about 10° C. to about 15° C., about 15° C. to about 20°C., about 20° C. to about 25° C., about 25° C. to about 30° C., about30° C. to about 35° C., about 35° C. to about 40° C., about 40° C. toabout 45° C., about 45° C. to about 50° C., about 50° C. to about 55°C., about 55° C. to about 60° C., about 60° C. to about 65° C., about65° C. to about 70° C., about 70° C. to about 75° C., about 75° C. toabout 80° C., about 80° C. to about 85° C., about 85° C. to about 90°C., about 90° C. to about 95° C., about 95° C. to about 100° C., or anyother value or range of values therein). In certain embodiments, theresultant mixture is agitated at ambient temperature (e.g., about 23°C.).

The resultant mixture is then allowed to stand without agitation toallow any undissolved or unsuspended solids to precipitate. Theresultant mixture can be allowed to stand at a temperature of from about5° C. to about 100° C. (e.g., about 5° C. to about 10° C., about 10° C.to about 15° C., about 15° C. to about 20° C., about 20° C. to about 25°C., about 25° C. to about 30° C., about 30° C. to about 35° C., about35° C. to about 40° C., about 40° C. to about 45° C., about 45° C. toabout 50° C., about 50° C. to about 55° C., about 55° C. to about 60°C., about 60° C. to about 65° C., about 65° C. to about 70° C., about70° C. to about 75° C., about 75° C. to about 80° C., about 80° C. toabout 85° C., about 85° C. to about 90° C., about 90° C. to about 95°C., about 95° C. to about 100° C., or any other value or range of valuestherein) for a period of about 10 minutes, about 20 minutes, about 30minutes, about 40 minutes, about 50 minutes, about 1 hour, about 2hours, about 3 hours, about 4 hours, about 8 hours, or any other valueor range of values therein or thereabove). In certain embodiments, afteradmixture with an additive, the resultant mixture is allowed to stand atambient temperature (e.g., about 23° C.), until any undissolved orunsuspended solids present have precipitated. The resultant mixture canthen be decanted or filtered to remove the solids therefrom, and thesolids are discarded, to provide the present aqueous composition in theform of a solvent mixture. The solvent mixture generally has a final pHranging from about 5 to about 14 (e.g., from about 5 to about 6, fromabout 6 to about 7, from about 7 to about 8, from about 8 to about 9,from about 9 to about 10, from about 10 to about 11, from about 11 toabout 12, from about 12 to about 13, from about 13 to about 14, or anyother value or range of values therein). In certain embodiments, the pHranges from about 6 to about 8. In other embodiments, the pH is about13. In certain embodiments, the pH of the solvent mixture ranges fromabout 5 to about 13; from about 6 to about 13; from about 7 to about 13;from about 8 to about 13; from about 9 to about 13; from about 10 toabout 13; from about 11 to about 13; from about 12 to about 13.

In certain embodiments, the resultant mixture can be further purifiedvia the application of gravity or another force that can effectseparation of one or more unwanted by-products (e.g., solids, gels,suspensions and the like) from the present aqueous compositions. Forexample, in some embodiments, the resultant mixture is subject tocentrifugal force effected by a centrifuge to remove one or moreunwanted by-products. The centrifugal force applied can be expressed interms of relative centrifugal force (RCF), as a number (n) times theforce of gravity (g), and has units of g, wherein 1 g is the force ofgravity at sea level. RCF can be a convenient value to use whendescribing the centrifugal force acting on a given material because itis a constant that is independent of the apparatus used. Thus, in someembodiments, the RCF applied to the resultant mixture is from about 100g to about 20,000 g (e.g., from about 10 g to about 1,000 g, from about1,000 g to about 2,000 g, from about 2,000 g to about 3,000 g, fromabout 3,000 g to about 4,000 g, from about 4,000 g to about 5,000 g,from about 5,000 g to about 6,000 g, from about 6,000 g to about 7,000g, from about 7,000 g to about 8,000 g, from about 8,000 g to about9,000 g, from about 9,000 g to about 10,000 g, from about 10,000 g toabout 11,000 g, from about 11,000 g to about 12,000 g, from about 12,000g to about 13,000 g, from about 13,000 g to about 14,000 g, from about14,000 g to about 15,000 g, from about 15,000 g to about 16,000 g, fromabout 16,000 g to about 17,000 g, from about 17,000 g to about 18,000 g,from about 18,000 g to about 19,000 g, from about 19,000 g to about20,000 g, or any other value or range of values therein). In someembodiments, the RCF ranges from about 12,000 g to about 18,000 g. Inother embodiments, the RCF ranges from about 15,000 g to about 18,000 g.After such centrifugation, the supernatant may be removed by, e.g.,suction, decantation, filtration and the like, to afford the presentaqueous compositions.

Extractants

The present compositions can be combined with water to form anextractant useful in the methods described herein. Thus, in anotherembodiment, the present invention relates to extractants comprisingabout 0.1 wt % to about 2 wt % of plant material, 0 to about 2 wt % of apolysaccharide, 0% to about 1 wt % of an alcohol, 0% to about 10 wt % ofa base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of an acid,0% to about 10 wt % of an additive, and about 90 wt % to about 99.9 wt %water. In some embodiments, the extractant comprises about 0.1 wt % toabout 1 wt % of plant material and 0 to about 1 wt % of apolysaccharide. In certain embodiments, the extractant comprises about0.1 wt % to about 0.5 wt % of plant material and 0 to about 1 wt % of apolysaccharide. In some embodiments, the extractant does not comprise apolysaccharide other than that present in or derived from the plantmaterial. In other embodiments, the aqueous compositions do not comprisea polysaccharide.

The polysaccharide can be present in the extractants in an amountranging from about 0 to about 2 wt % (e.g., about 0.01 wt % to about0.05 wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt % to about0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % to about 0.4wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt % to about 1.0 wt%, about 1.0 wt % to about 1.5 wt %, about 1.5 wt % to about 2.0 wt %,or any other value or range of values therein). In some embodiments, thepolysaccharide is present in an amount of from 0 wt % to about 1 wt %.In other embodiments, the present extractants do not comprise apolysaccharide other than that present in or derived from the plantmaterial. When present, polysaccharides which are useful in the presentextractants include those as described herein which can be employed inthe present aqueous compositions.

In some embodiments, the plant material is present in the extractants inan amount ranging from about 0.1 to about 2 wt % (e.g., about 0.01 wt %to about 0.05 wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt % toabout 0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % toabout 0.4 wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt % toabout 0.6 wt %, about 0.6 wt % to about 0.7 wt %, about 0.7 wt % toabout 0.8 wt %, about 0.8 wt % to about 0.9 wt %, about 0.9 wt % toabout 1.0 wt %, about 1.0 wt % to about 1.5 wt %, about 1.5 wt % toabout 2.0 wt %, or any other value or range of values therein). Plantmaterials which are useful in the present extractant include those asdescribed herein which can be employed in the present aqueouscompositions. In some embodiments, the plant material is present in anamount of from about 0.1 wt % to about 1 wt %. In certain embodiments,the plant material is present in an amount of from about 0.1 wt % toabout 0.5 wt %.

The present extractants can further comprise an acid or a base. Acidsand bases useful in the present extractants are those as describedhereinabove which are useful in the present aqueous compositions. Theacid can be present in the extractants in an amount from 0 wt % to about1 wt % (e.g., about 0 to about 0.01 wt %, about 0.01 wt % to about 0.05wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt % to about 0.2 wt%, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % to about 0.4 wt %,about 0.4 wt % to about 0.5 wt %, about 0.5 wt % to about 0.6 wt %,about 0.6 wt % to about 0.7 wt %, about 0.7 wt % to about 0.8 wt %,about 0.8 wt % to about 0.9 wt %, about 0.9 wt % to about 1 wt %, or anyother value or range of values therein). In some embodiments, the acidis present from about 0.01 wt % to about 1 wt % of the extractant. Insome embodiments, the extractant does not comprise an acid.

The base can be present in the extractants in an amount from 0 wt % toabout 1 wt % (e.g., about 0 to about 0.01 wt %, about 0.01 wt % to about0.05 wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt % to about0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % to about 0.4wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt % to about 0.6 wt%, about 0.6 wt % to about 0.7 wt %, about 0.7 wt % to about 0.8 wt %,about 0.8 wt % to about 0.9 wt %, about 0.9 wt % to about 1 wt %, or anyother value or range of values therein). In some embodiments, the baseis present from about 0.01 wt % to about 1 wt % of the extractants. Insome embodiments, the extractant does not comprise a base.

The present extractants can also comprise a salt. Salts useful in thepresent extractants are those as described hereinabove which are usefulin the present aqueous compositions. The salt can be present in theextractants in an amount from 0 wt % to about 1 wt % (e.g., about 0 toabout 0.01 wt %, about 0.01 wt % to about 0.05 wt %, about 0.05 wt % toabout 0.1 wt %, about 0.1 wt % to about 0.2 wt %, about 0.2 wt % toabout 0.3 wt %, about 0.3 wt % to about 0.4 wt %, about 0.4 wt % toabout 0.5 wt %, about 0.5 wt % to about 0.6 wt %, about 0.6 wt % toabout 0.7 wt %, about 0.7 wt % to about 0.8 wt %, about 0.8 wt % toabout 0.9 wt %, about 0.9 wt % to about 1 wt %, or any other value orrange of values therein). In some embodiments, the salt is present fromabout 0.01 wt % to about 1 wt % of the extractant. In some embodiments,the extractant does not comprise a salt.

The present extractants can further comprise an organic solvent. Organicsolvents which can be present in the extractants include those describeabove which can be present in the aqueous compositions of the invention.The amount of organic solvent, if present, can be in an amount of 0 wt %to about 1 wt % (e.g., about 0 to about 0.01 wt %, about 0.01 wt % toabout 0.05 wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt % toabout 0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % toabout 0.4 wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt % toabout 0.6 wt %, about 0.6 wt % to about 0.7 wt %, about 0.7 wt % toabout 0.8 wt %, about 0.8 wt % to about 0.9 wt %, about 0.9 wt % toabout 1 wt %, or any other value or range of values therein). In someembodiments, the extractant dos not comprise an organic solvent. In someembodiments, the extractant dos not comprise an alcohol.

The present extractants can also comprise one or more other additives.Additives that can be present in the extractants include those describeabove which can be present in the aqueous compositions of the invention.The additive(s) can be present in the extractants in amounts rangingfrom 0 to about 1 wt % (e.g., about 0 to about 0.01 wt %, about 0.01 wt% to about 0.05 wt %, about 0.05 wt % to about 0.1 wt %, about 0.1 wt %to about 0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3 wt % toabout 0.4 wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt % toabout 0.6 wt %, about 0.6 wt % to about 0.7 wt %, about 0.7 wt % toabout 0.8 wt %, about 0.8 wt % to about 0.9 wt %, about 0.9 wt % toabout 1 wt %, or any other value or range of values therein). In certainembodiments, the additive is Type-S hydrated lime. In some embodiments,the extractant dos not comprise an additive. In some embodiments, theextractant does not comprise lime. In some embodiments, the extractantdoes not comprise Type-S hydrated lime.

The amount of water in the present extractants can range from about 90to about 99.9 wt % (e.g., about 90 wt % to about 91 wt %, about 91 wt %to about 92 wt %, about 92 wt % to about 93 wt %, about 93 wt % to about94 wt %, about 94 wt % to about 95 wt %, about 95 wt % to about 96 wt %,about 96 wt % to about 97 wt %, about 97 wt % to about 98 wt %, about 98wt % to about 99 wt %, about 99 wt % to about 99.5 wt %, about 99.5 wt %to about 99.9 wt %, or any other value or range of values therein). Incertain embodiments, the extractant comprises from about 95 wt % toabout 99.9% wt % water.

In particular embodiments of the present invention, the extractantscomprise a polysaccharide that is guar gum and plant material that iscorn gluten meal. In other embodiments of the present invention, theextractants comprise plant material that is corn gluten meal and doesnot contain a polysaccharide other than that present in the corn glutenmeal. In other embodiments, the extractants optionally further compriseone or more of water, isopropanol, citric acid, Type S hydrated lime,sodium hydroxide, and sodium chloride.

Thus, in some embodiments, the present invention extractants comprisingabout 0.1 wt % to about 2 wt % of plant material, 0 to about 2 wt % of apolysaccharide, 0% to about 1 wt % of an alcohol, 0% to about 10 wt % ofa base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of an acid,0% to about 10 wt % of an additive, and about 90 wt % to about 99.9 wt %water. In certain embodiments, the extractant comprises from about 0.1wt % to about 1 wt % of the plant material and 0 to about 1 wt % of thepolysaccharide. In certain embodiments, the extractant comprises about0.1 wt % to about 0.5 wt % of the plant material and 0 to about 0.1 wt %of the polysaccharide. In some embodiments, the plant material comprisesplant protein. In some embodiments, the plant proteins are prolamines.In some embodiments, the plant of the extractant is a cereal. In certainembodiments, the cereal is corn, rice, wheat, barley, sorghum, millet,rye, triticale, fonio, buckwheat, wheat grass, wheat, spelt or quinoa.In certain embodiments, the cereal is corn. In other embodiments, theplant material is lentils (e.g., green, yellow, black), hemp seed, chia,grass, wheat grass and barley (e.g., pearl, groat). In some embodiments,the polysaccharide of the extractant is alginate, carrageenan, gumArabic, tragacanth gum, guar gum, pectin, ghatti gum, xanthan gum, ormixtures thereof. In certain embodiments, the extractant does notcomprise polysaccharide other than that present in or derived from theplant material. In certain embodiments, the extractant does not compriseany of the aforementioned polysaccharides other than that present in orderived from the plant material. In certain embodiments, thepolysaccharide is about 0.05 wt % to about 0.2 wt % of the extractant.In some embodiments, the extractant does not comprise polysaccharide.

In some embodiments, the extractant further comprises an alcohol. Incertain embodiments, the alcohol is ethanol, methanol, or isopropanol.In one embodiment, the alcohol is isopropanol. In some embodiments, thealcohol is about 0 wt % to about 1 wt % of the extractant. In someembodiments, the extractant does not comprise an alcohol.

In certain embodiments, the extractant further comprises a base. Inother embodiments, the base is an inorganic base or an inorganic base.In some embodiments, the inorganic base is an alkali metal or alkalineearth metal base. In certain embodiments, the inorganic base is sodiumhydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate,potassium carbonate, sodium bicarbonate, potassium bicarbonate,magnesium carbonate or calcium carbonate. In one embodiment, the base is0 wt % to about 1 wt % of the extractant. In some embodiments, theextractant does not comprise a base.

In certain embodiments, the extractant further comprises a salt. In someembodiments, the salt is sodium chloride, potassium chloride, calciumchloride, magnesium chloride, ammonium chloride, sodium bromide,potassium bromide, calcium bromide, magnesium bromide, ammonium bromide,sodium iodide, potassium iodide, calcium iodide, magnesium iodide,ammonium iodide, sodium sulfate, potassium sulfate, calcium sulfate,magnesium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate,magnesium nitrate, calcium nitrate, ammonium nitrate or mixturesthereof. In certain embodiments, the salt is 0 wt % to about 1 wt % ofthe extractant. In some embodiments, the extractant does not comprise asalt.

In certain embodiments, the extractant further comprises an acid. Inother embodiments, the acids include inorganic acids. In certainembodiments, the inorganic acids include carbonic acid, sulfuric acid,or hydrochloric acid. In some embodiments, the acid is an organic acid.In certain embodiments, the acid is a C1-C20 organic acid. In otherembodiments, the acid is citric acid, formic acid, ascorbic acid, aceticacid, malic acid, adipic acid, tannic acid, lactic acid, fumaric acid,or mixtures thereof. In one embodiment, the acid is citric acid. Incertain embodiments, the acid is 0 wt % to about 1 wt % of theextractant. In some embodiments, the extractant does not comprise anacid.

In some embodiments, the extractant further comprises an additive. Incertain embodiments, the additive is lime. In one embodiment, the limeis Type S Hydrated Lime. In some embodiments, the extractant does notcomprise an additive. In certain embodiments, the Type S Hydrated Limeis 0 wt % to about 1 wt % of the extractant. In some embodiments, theextractant does not comprise lime. In some embodiments, the extractantdoes not comprise S type hydrated lime. In certain embodiments, theextractant comprises about 95 wt % to about 99 wt % water. In someembodiments, the pH of the extractant is from about 5 to about 14. Incertain embodiments, the pH of the extractant is from about 6 to about8. In certain embodiments, the pH of the extractant ranges from about 5to about 13; from about 6 to about 13; from about 7 to about 13; fromabout 8 to about 13; from about 9 to about 13; from about 10 to about13; from about 11 to about 13; from about 12 to about 13. In certainembodiments, the extractant does not comprise a polysaccharide otherthan that present in or derived from the plant material. In oneembodiment, the extractant does not comprise a polysaccharide other thanthat derived from the plant material, the plant material is corn glutenmeal, and the aqueous composition further comprises isopropanol, citricacid, Type S hydrated lime, sodium hydroxide, and sodium chloride. Incertain embodiments, the extractant further comprises a substrate.

Preparation of the Extractants

The present extractants can be made by adding water to the aqueouscompositions of the invention as described herein. A desired waterpercentage of the present extractants can be selected in view of aparticular application, such as oil sand extraction, coal tarextraction, hydraulic fracturing, soil remediation, or spill cleanup asdescribed hereinbelow.

Thus, in one embodiment, the present invention provides method formaking an extractant comprising about 0.1 wt % to about 2 wt % of plantmaterial, 0 to about 2 wt % of a polysaccharide, 0% to about 1 wt % ofan alcohol, 0% to about 10 wt % of a base, 0% to about 10 wt % of asalt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and about 90 wt % to about 99.9 wt % water, comprising addingwater to an aqueous composition of the present invention in an amount offrom about 90 wt % to about 99.9 wt %. In certain embodiments, themethod comprises preparing an extractant comprising about 0.1 wt % toabout 2 wt % of plant material, 0 to about 2 wt % of a polysaccharide,0% to about 1 wt % of an alcohol, 0% to about 10 wt % of a base, 0% toabout 10 wt % of a salt, 0% to about 10 wt % of an acid, 0% to about 10wt % of an additive, and about 90 wt % to about 99.9 wt % water,comprising adding water to a substantially anhydrous composition asdescribed herein in an amount of from about 90 wt % to about 99.9 wt %.

Substantially Anhydrous Compositions

The present aqueous compositions or extractants can be dried to form asubstantially anhydrous composition. “Substantially anhydrous” meansthat the compositions comprise no more than about 10% water; in anotherembodiment, no more than about 5% water; in another embodiment, no morethan about 2% water; in another embodiment, no more than about 1% waterby weight of the composition; in another embodiment, no more than about0.5% water by weight of the composition; and in another embodiment, nomore than about 0.1% by weight of the composition.

Thus, in another aspect, the present invention relates to substantiallyanhydrous compositions comprising about 20 wt % to about 99.9 wt % ofplant material, 0 to about 20 wt %, of a polysaccharide, 0% to about 1wt % of an alcohol, 0% to about 50 wt % of a base, 0% to about 10 wt %of a salt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and 0% to about 10 wt % water. The plant material and, ifpresent, the polysaccharide of the present substantially anhydrouscompositions can be present in relative amounts such that they form acomplex. Polysaccharides which are useful in the present substantiallyanhydrous compositions include those as described herein. In someembodiments, the present substantially anhydrous compositions do notcomprise polysaccharide other than that derived from the plant material.In other embodiments, the present substantially anhydrous compositionsdo not comprise polysaccharide.

The polysaccharide can be present in the substantially anhydrouscompositions in an amount ranging from about 0 to about 20 wt % (e.g., 0to about 0.5 wt %, about 0.5 wt % to about 1 wt %, about 1 wt % to about2 wt %, about 2 wt % to about 3 wt %, about 3 wt % to about 4 wt %,about 4 wt % to about 5 wt %, about 5 wt % to about 6 wt %, about 6 wt %to about 7 wt %, about 7 wt % to about 8 wt %, about 8 wt % to about 9wt %, about 9 wt % to about 10 wt %, about 10 wt % to about 11 wt %,about 11 wt % to about 12 wt %, about 12 wt % to about 13 wt %, about 13wt % to about 14 wt %, about 14 wt % to about 15 wt %, about 15 wt % toabout 16 wt %, about 16 wt % about 17 wt %, about 17 wt % to about 18 wt%, about 18 wt % to about 19 wt %, about 19 wt % to about 20 wt %, orany other value or range of values therein). In some embodiments, thepolysaccharide is present in an amount of from 0 wt % to about 10 wt %.In other embodiments, the present substantially anhydrous compositionsdo not comprise a polysaccharide other than that present in or derivedfrom the plant material. When present, polysaccharides that are usefulin the present substantially anhydrous compositions include those asdescribed herein.

In some embodiments, the plant material is present in the substantiallyanhydrous compositions in an amount ranging from about 20 wt % to about99.9 wt % (e.g., about 20 wt % to about 25 wt %, about 25 wt % to about30 wt %, about 30 wt % to about 35 wt %, about 35 wt % to about 40 wt %,about 40 wt % to about 45 wt %, about 45 wt % to about 50 wt %, about 50wt % to about 55 wt %, about 55 wt % to about 60 wt %, about 60 wt % toabout 65 wt %, about 65 wt % to about 70 wt %, about 70 wt % to about 75wt %, about 75 wt % to about 80 wt %, about 80 wt % to about 85 wt %,about 85 wt % to about 90 wt %, about 90 wt % to about 91 wt %, about 91wt % to about 92 wt %, about 92 wt % to about 93 wt %, about 93 wt % toabout 94 wt %, about 94 wt % to about 95 wt %, about 95 wt % to about 96wt %, about 96 wt % to about 97 wt %, about 97 wt % to about 98 wt %,about 98 wt % to about 99 wt %, about 99 wt % to about 99.5 wt %, about99.5 wt % to about 99.9 wt %, or any other value or range of valuestherein). Plant materials which are in the present substantiallyanhydrous compositions include those as described herein. In someembodiments, the plant material is present in an amount of from about 85wt % to about 99.9 wt %. In certain embodiments, the plant material ispresent in an amount of from about 95 wt % to about 99.9 wt %. In someembodiments, the plant material comprises a plant protein.

The present substantially anhydrous compositions can further comprise anacid or a base. Acids and bases useful in the present substantiallyanhydrous compositions are those as described hereinabove. The acid canbe present in the substantially anhydrous compositions in an amount from0 wt % to about 10 wt % (e.g., 0 to about 0.5 wt %, about 0.5 wt % toabout 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % to about 3 wt%, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt %, about 5wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7 wt % toabout 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % to about 10 wt%, or any other value or range of values therein). In some embodiments,the acid is present from about 0.01 wt % to about 2 wt % of thesubstantially anhydrous compositions. In some embodiments, thesubstantially anhydrous compositions do not comprise an acid.

The base can present in the substantially anhydrous compositions in anamount from 0 wt % to about 50 wt % (e.g., 0 to about 0.5 wt %, about0.5 wt % to about 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % toabout 3 wt %, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt%, about 5 wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7wt % to about 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % toabout 10 wt %, about 10 wt % to about 15 wt %, about 15 wt % to about 20wt %, about 20 wt % to about 25 wt %, about 25 wt % to about 30 wt %,about 30 wt % to about 35 wt %, about 35 wt % to about 40 wt %, about 40wt % to about 45 wt %, about 45 wt % to about 50 wt %, or any othervalue or range of values therein). In some embodiments, the base ispresent from about 0.01 wt % to about 5 wt % of the substantiallyanhydrous compositions.

The substantially anhydrous compositions can also comprise a salt. Saltsuseful in the substantially anhydrous compositions are those asdescribed hereinabove. The salt can be present in the substantiallyanhydrous compositions in an amount from 0 wt % to about 10 wt % (e.g.,0 to about 0.5 wt %, about 0.5 wt % to about 1 wt %, about 1 wt % toabout 2 wt %, about 2 wt % to about 3 wt %, about 3 wt % to about 4 wt%, about 4 wt % to about 5 wt %, about 5 wt % to about 6 wt %, about 6wt % to about 7 wt %, about 7 wt % to about 8 wt %, about 8 wt % toabout 9 wt %, about 9 wt % to about 10 wt %, or any other value or rangeof values therein). In some embodiments, the salt is present from about0.01 wt % to about 1 wt % of the substantially anhydrous compositions.In some embodiments, the substantially anhydrous compositions do notcomprise a salt.

As stated above, the substantially anhydrous compositions can comprisewater. The amount of water in the substantially anhydrous compositionscan range from 0 to about 10 wt % (e.g., 0 to about 0.5 wt %, about 0.5wt % to about 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % toabout 3 wt %, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt%, about 5 wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7wt % to about 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % toabout 10 wt %, or any other value or range of values therein). Incertain embodiments, the substantially anhydrous compositions compriseless than about 5 wt % water (e.g., less than about 4 wt %, less thanabout 3 wt %, less than about 2 wt %, less than about 1 wt % less thanabout 0.9 wt %, less than about 0.8 wt %, less than about 0.7 wt %, lessthan about 0.6 wt %, less than about 0.5 wt %, less than about 0.4 wt %,less than about 0.3 wt %, less than about 0.2 wt %, less than about 0.1wt %, or any other value or range of values therein or therebelow).

The substantially anhydrous compositions can further comprise an organicsolvent. Organic solvents which can be present in the substantiallyanhydrous compositions include those described above. The amount oforganic solvent, if present, can be in an amount of 0 wt % to about 1 wt% (e.g., 0 to about 0.05 wt %, about 0.05 wt % to about 0.1 wt %, about0.1 wt % to about 0.2 wt %, about 0.2 wt % to about 0.3 wt %, about 0.3wt % to about 0.4 wt %, about 0.4 wt % to about 0.5 wt %, about 0.5 wt %to about 0.6 wt %, about 0.6 wt % to about 0.7 wt %, about 0.7 wt % toabout 0.8 wt %, about 0.8 wt % to about 0.9 wt %, about 0.9 wt % toabout 1.0 wt %, or any other value or range of values therein). Incertain embodiments, the substantially anhydrous compositions do notcomprise organic solvent.

The substantially anhydrous compositions can also comprise one or moreother additives. Additives that which can be present in thesubstantially anhydrous compositions include those described above. Theadditive(s) can be present in the substantially anhydrous compositionsin amounts ranging from 0 to about 10% (e.g., 0 to about 0.5 wt %, about0.5 wt % to about 1 wt %, about 1 wt % to about 2 wt %, about 2 wt % toabout 3 wt %, about 3 wt % to about 4 wt %, about 4 wt % to about 5 wt%, about 5 wt % to about 6 wt %, about 6 wt % to about 7 wt %, about 7wt % to about 8 wt %, about 8 wt % to about 9 wt %, about 9 wt % toabout 10 wt %, or any other value or range of values therein). Incertain embodiments, the additive is Type-S hydrated lime. In someembodiments, the substantially anhydrous compositions do not comprise anadditive. In some embodiments, the substantially anhydrous compositionsdo not comprise lime.

In particular embodiments of the present invention, the substantiallyanhydrous compositions comprise a polysaccharide that is guar gum andplant material that is corn gluten meal. In other embodiments of thepresent invention, the substantially anhydrous compositions compriseplant material that is corn gluten meal and do not comprise apolysaccharide other than that present in or derived from the corngluten meal. In other embodiments, the substantially anhydrouscompositions comprise one or more of water, isopropanol, citric acid,Type S hydrated lime, sodium hydroxide, and sodium chloride.

Thus, in certain embodiments the present invention providessubstantially anhydrous compositions comprising about 20 wt % to about99.9 wt % of plant material, 0 to about 20 wt %, of a polysaccharide, 0%to about 1 wt % of an alcohol, 0% to about 50 wt % of a base, 0% toabout 10 wt % of a salt, 0% to about 10 wt % of an acid, 0% to about 10wt % of an additive, and 0% to about 10 wt % water. In certainembodiments, the substantially anhydrous composition comprises about 85wt % to about 99.9 wt % of the plant material and 0 to about 10 wt % ofthe polysaccharide. In other embodiments, the substantially anhydrouscomposition of comprises about 95 wt % to about 99.9 wt % of the plantmaterial and 0 to about 5 wt % of the polysaccharide. In certainembodiments, plant is a cereal. In other embodiments, the cereal iscorn, rice, wheat, barley, sorghum, millet, rye, triticale, fonio,buckwheat, spelt or quinoa. In certain embodiments, the cereal is corn.In some embodiments, the plant material is corn gluten meal. In certainembodiments, the plant is cotton. In some embodiments the plant materialcomprises a plant protein. In other embodiments, the plant protein isprolamine, zein, hordein, or gliadin.

In some embodiments, the substantially anhydrous composition comprises apolysaccharide which is alginate, carrageenan, gum Arabic, tragacanthgum, guar gum, pectin, ghatti gum, xanthan gum, or mixtures thereof. Inother embodiments, the substantially anhydrous composition does notcomprise one or more of the aforementioned polysaccharides. In certainembodiments, the polysaccharide is 0 wt % to about 20 wt % of thesubstantially anhydrous composition. In other embodiments, thesubstantially anhydrous composition does not comprise polysaccharideother than that present in or derived from the plant material. In someembodiments, the substantially anhydrous composition further comprisesan alcohol. In one embodiments, the alcohol is ethanol, methanol, orisopropanol. In other embodiments, the alcohol is isopropanol. Incertain embodiments, the alcohol is about 0 wt % to about 1 wt % of thesubstantially anhydrous composition. In some embodiments, substantiallyanhydrous composition does not comprise an alcohol.

In certain embodiments, the substantially anhydrous composition furthercomprises a base. In some embodiments, the base is an inorganic base oran inorganic base. In certain embodiments, inorganic base is an alkalimetal or alkaline earth metal base. In certain embodiments, theinorganic base is sodium hydroxide, lithium hydroxide, or potassiumhydroxide. In certain embodiments, the base is 0 wt % to about 10 wt %of the substantially anhydrous composition. In some embodiments,substantially anhydrous composition does not comprise a base.

In certain embodiments, the substantially anhydrous composition furthercomprises a salt. In some embodiments, the salt is sodium chloride,potassium chloride, calcium chloride, magnesium chloride, ammoniumchloride, sodium bromide, potassium bromide, calcium bromide, magnesiumbromide, ammonium bromide, sodium iodide, potassium iodide, calciumiodide, magnesium iodide, ammonium iodide, sodium sulfate, potassiumsulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, potassiumnitrate, calcium nitrate, magnesium nitrate, ammonium nitrate, ormixtures thereof. In certain embodiments, the salt is 0 wt % to about 10wt % of the substantially anhydrous composition. In some embodiments,substantially anhydrous composition does not comprise a salt.

In some embodiments, the substantially anhydrous composition furthercomprises an acid. In other embodiments, the acids include inorganicacids. In certain embodiments, the inorganic acids include carbonicacid, sulfuric acid, or hydrochloric acid. In some embodiments, the acidis an organic acid. In certain embodiments, the acid is a C1-C20 organicacid. In certain embodiments, the acid is citric acid, formic acid,ascorbic acid, acetic acid, malic acid, adipic acid, tannic acid, lacticacid, fumaric acid, or mixtures thereof. In other embodiments, the acidis citric acid. In some embodiments, the acid is 0 wt % to about 10 wt %of the substantially anhydrous composition. In some embodiments,substantially anhydrous composition does not comprise an acid.

In certain embodiments, the substantially anhydrous composition furthercomprises an additive. In some embodiments, the additive is lime. Incertain embodiments, the lime is Type S Hydrated Lime. In certainembodiments, the Type S Hydrated Lime is 0 wt % to about 10 wt % of thesubstantially anhydrous composition. In some embodiments, substantiallyanhydrous composition does not comprise an additive. In someembodiments, substantially anhydrous composition does not comprise lime.

In some embodiments, the substantially anhydrous composition comprises 0wt % to about 10 wt % water. In other embodiments, the substantiallyanhydrous composition comprises 0 wt % to about 1 wt % water. In someembodiments, the substantially anhydrous composition does not comprise apolysaccharide other than the present in or derived from the plantmaterial.

Preparation of the Substantially Anhydrous Compositions

The aqueous compositions or extractants described herein can bedehydrated to form the present substantially anhydrous compositions. Thesubstantially anhydrous compositions can later be reconstituted with asuitable solvent as described herein to provide the aqueous compositionsor extractants. This allows for preparation of substantially anhydrouscompositions, which can be easier and or less costly to handle, maintainor store. For example, once the present aqueous compositions orextractants as described herein have been prepared, their solvent can beremoved to yield a substantially anhydrous composition. In preparing thepresent substantially anhydrous compositions, an acid or base asdescribed herein can be added to adjust the pH prior to solvent removal.For example, the pH can be adjusted to from about 5 to about 14 (e.g.,from about 5 to about 6, from about 6 to about 7, from about 7 to about8, from about 8 to about 9, from about 9 to about 10, from about 10 toabout 11, from about 11 to about 12, from about 12 to about 13, fromabout 13 to about 14, or any other value or range of values therein).

Any number of solvent removal techniques useful for obtaining asubstantially anhydrous composition, e.g., from an aqueous compositionor extractant can be used to prepare the prepare the substantiallyanhydrous compositions, including, but not limited to, vacuum drying,centrifugation, evaporation, freeze drying, air drying, lyophilization,convection oven drying or a combination thereof. One method for removingthe solvent is vacuum drying, which safely removes and recovers thesolvent while drying the product to provide the present substantiallyanhydrous compositions. The substantially anhydrous compositions can befurther processed by grinding or milling to a desired mesh particlesize. The substantially anhydrous compositions can also be subjected toparticle-size reduction to form, for example, powders. The substantiallyanhydrous compositions can be subsequently admixed with water or organicsolvent to provide a reconstituted aqueous composition or extractant forimmediate or later use.

Thus, in certain embodiments, the present invention provides a method ofmaking a substantially anhydrous composition comprising about 20 wt % toabout 99.9 wt % of plant material, 0 to about 20 wt %, of apolysaccharide, 0% to about 1 wt % of an alcohol, 0% to about 50 wt % ofa base, 0% to about 10 wt % of a salt, 0% to about 10 wt % of an acid,0% to about 10 wt % of an additive, and 0% to about 10 wt % water,comprising removing water from an aqueous composition of the presentinvention. In certain embodiments, removing water comprises drying. Incertain embodiments, drying comprises heating the aqueous composition orsubjecting the aqueous composition to reduced pressure. In someembodiments, the invention provides a method of making a substantiallyanhydrous composition comprising about 20 wt % to about 99.9 wt % ofplant material, 0 to about 20 wt %, of a polysaccharide, 0% to about 1wt % of an alcohol, 0% to about 50 wt % of a base, 0% to about 10 wt %of a salt, 0% to about 10 wt % of an acid, 0% to about 10 wt % of anadditive, and 0% to about 10 wt % water, comprising removing water froman extractant of the present invention. In some embodiments, removingwater from the extractant comprises drying the extractant. In someembodiments, drying comprises heating the extractant or subjecting theextractant to reduced pressure.

Methods

In one aspect the present invention provides methods for extracting ahydrocarbon-containing substance from a substrate, comprising contactingthe substrate with an aqueous composition or extractant under conditionseffective for extracting at least some of the hydrocarbon-containingsubstance from the substrate. In one embodiment, “extracting” as usedherein includes removing a hydrocarbon-containing substance from thesurface of a substrate. In another embodiment, “extracting” as usedherein includes extracting the hydrocarbon-containing substance frompores, fractures, cracks, fissures, crevices or interstitial spaces of asubstrate.

In some embodiments, the hydrocarbon-containing substance is grease oroil, including heavy oil, crude oil, refined oil, shale oil, bitumen,coal tar, synthetic oil, and fractions or products thereof; automotiveoil; oil from oil sand, for example, from Athabasca, Venezuela or Utahoil sand; oil obtained from hydraulic fracturing; and oil from the skinof an animal. In other embodiments, the hydrocarbon-containing substancecomprises natural gas liquids.

In certain embodiments, the substrate is soil, sand, beach sand, oilsand, heavy-oil sand, rock, wood, paper, skin, water, gravel, mud, clay,plant, hair, fabric, class, porcelain, concrete or metal. The substratecan be a solid or a liquid. Where the substrate is a solid, it can be asolid comprising a pore, fracture, crack, fissure or crevice; a smooth,non-porous solid; or a particulate material such as a powder, sand,gravel, silt or sediment.

In certain embodiments, the substrate is water. In one embodiment, thesubstrate is a waterbody. A waterbody can include ponds, lakes, streams,rivers, oceans, seawater, fresh water, salt water, brackish water,groundwater, wastewaster, and the like. Accordingly, in one embodiment,the substrate is a waterbody. In this regard, a hydrocarbon-containingsubstance can be extracted from a waterbody by treating it with apresent aqueous composition or extractant. In certain embodiments, thesubstrate is soil. In other embodiments, the substrate is sediment. Inother embodiments, the substrate is metal. In one embodiment, thesubstrate is a metal storage tank. In another embodiment, the substrateis a metal pipe. In another embodiment, the substrate is glass. Inanother embodiment, the substrate is porcelain. In another embodiment,the substrate is a concrete.

In one embodiment, the substrate is fabric. Fabric can include any wovenmaterial or fibers, including natural fibers such as cotton, wool,linen, silk, hemp, jute, etc., and synthetic fibers including rayon,polyester, nylon, etc. Thus, in certain embodiments, the present methodsmay be employed to extract a hydrocarbon-containing substance fromfabric or woven materials. In some embodiments, the present inventionprovides a laundry detergent comprising a Composition of the Invention.In certain embodiments, the present invention provides a method forextracting a hydrocarbon-containing substance from fabric comprisingcontacting the fabric with a laundry detergent comprising a Compositionof the Invention.

Accordingly, in another aspect, the present invention provides laundrydetergents comprising an aqueous composition of the present invention.In some embodiments, the laundry detergent comprises an extractant ofthe present invention. In other embodiments, the laundry detergentcomprises a substantially anhydrous composition of the presentinvention. In some embodiments, the invention further provides a methodfor removing a hydrocarbon-containing substance from fabric comprisingcontacting the fabric with the laundry detergent comprising aComposition of the Invention

The present methods can be performed at less-than elevated temperature(e.g., at about 23° C.). However, in certain embodiments, it can beadvantageous to heat a mixture of an aqueous composition or extractantand a substrate to improve or accelerate extraction or remediation.Thus, the present methods can be performed at a temperature of fromabout 5° C. to about 100° C. (e.g., about 5° C. to about 10° C., about10° C. to about 15° C., about 15° C. to about 20° C., about 20° C. toabout 25° C., about 25° C. to about 30° C., about 30° C. to about 35°C., about 35° C. to about 40° C., about 40° C. to about 45° C., about45° C. to about 50° C., about 50° C. to about 55° C., about 55° C. toabout 60° C., about 60° C. to about 65° C., about 65° C. to about 70°C., about 70° C. to about 75° C., about 75° C. to about 80° C., about80° C. to about 85° C., about 85° C. to about 90° C., about 90° C. toabout 95° C., about 95° C. to about 100° C., or any other value or rangeof values therein).

The present methods are also useful for extractinghydrocarbon-containing substance (e.g., crude oil) from the skin of ananimal, such as a fish, bird or mammal, for example, after an oil spill.Thus, in certain embodiments, the animal is a living animal. In otherembodiments, the animal is a dead animal, which might be cleaned ordecontaminated.

According to the present invention, extracting a hydrocarbon-containingsubstance comprises contacting the substrate with an aqueous compositionor extractant under conditions that are effective for extracting atleast some of the hydrocarbon-containing substance from the substrate. Ahydrocarbon-containing substance comprises one or more hydrocarbons. Insome embodiments, the hydrocarbon is aromatic, such as benzene, toluene,naphthalene, xylene and a polycyclic aromatic hydrocarbon (PAH).Illustrative PAHs include naphthalene, fluorene, phenanthrene, pyrene,chrysene, and C₁-C₁₀ homologs thereof. A C₁ homolog of a PAH is a PAHhaving a methyl group. A C₂ homolog of a PAH is a PAH having, forexample, an ethyl group or two methyl groups. A C₃ homolog of a PAH is aPAH having, for example, a methyl and an ethyl group, three methylgroups, an n-propyl group or an i-propyl group. A C₄ homolog of a PAH isa PAH having, for example, two ethyl groups, four methyl groups, anethyl group and two methyl groups, a methyl group and an n-propyl group,a methyl group and an i-propyl group, an n-butyl group, a sec-butylgroup, and i-butyl group or a t-butyl group. In other embodiments, thehydrocarbon comprises one or more heteroatoms such as oxygen, nitrogenand sulfur. In some embodiment, the hydrocarbon is a heteroaromaticcompound such as pyridine, pyrazine, quinoline, furan, or thiophene, ora polycyclic aromatic compound optionally comprising one or moreheteroatoms such as N, O or S.

In other embodiments, the hydrocarbon is nonaromatic, such as acycloalkane, cycloalkene, and straight-branched-chain alkane, alkene andalkyne. In some embodiments, the non-aromatic hydrocarbon is a linear,branched or cyclic pentane, hexane, heptane, octane, nonane, or C₁₀-C₂₀alkane. In other embodiments, the hydrocarbon is a heteroatom-containingpartially or fully saturated linear, branched, cyclic or caged compound.In some embodiments, the hydrocarbon comprises an ester, an amide, anamine, an imine, a carboxylic acid, a sulfide, a sulfoxide, a sulfone, anitroxide or a nitrone moiety. In other embodiments, the hydrocarboncomprises a halogen. In some embodiments, the hydrocarbon-containingsubstance is an oil. Such oils include light oils having an API(American Petroleum Institute) gravity higher than 31.1° API (i.e., adensity of less than 870 kg/m³), medium oils having an API gravitybetween 22.3° API and 31.1° API (i.e., a density of from 870 kg/m³ to920 kg/m³), heavy oils having an API gravity below 22.3° API to 10.0°API (i.e., a density of from 920 kg/m³ to 1000 kg/m³), or extra heavyoil having an API gravity below 10.0° API (i.e., a density of greaterthan 1000 kg/m³). Thus, light, medium and heavy oils are less dense thanwater, whereas extra heavy oil is more dense than water. In someembodiments, the oil is a light tar oil. A light tar oil is an oilhaving an API gravity of 22.3° API to 10.0° API.

In other embodiments, the hydrocarbon-containing substance is coal tar.“Coal tar” as used herein refers to a dense non-aqueous phase liquid(DNAPL) which comprises mixture of highly aromatic hydrocarbons, wherethe mixture optionally comprises aliphatic hydrocarbons. Coal tar istypically a brown or black liquid having a very high viscosity, and isgenerally not pourable from a vessel at ambient temperatures. Coal taris one by-product of the manufacture of coke from coal, or fromgasification of coal. Coal tar can be complex or variable mixtures andcan comprise one of more phenols, polycyclic aromatic hydrocarbons(PAHs), and heterocyclic compounds. “Coal tar sand” as used herein is amixture of sand and coal tar, e.g., sand coated with coal tar, or coaltar with sand mixed or embedded therein.

In other embodiments, the hydrocarbon-containing substance is sludge,e.g., from a storage tank employed for storing industrial sewage orother waste materials. Such sludge can comprise anyhydrocarbon-containing substance as described herein, including lightoils, medium oils, heavy oils, extra-heavy oils, bitumen, or coal tar asdescribed herein, in addition to sediment such as sand, silt or clay,metals or waxes. An oil-contaminated sludge is a sludge as whichcomprises an oil.

In certain embodiments, the oil is crude oil. In some embodiments, thecrude oil is a sweet crude oil (oil having relatively low sulfurcontent, e.g., less than about 0.42% sulfur). In other embodiments, thecrude oil is a sour crude oil (oil having relatively high sulfur contente.g., about 0.42% or more sulfur). In some embodiments, thehydrocarbon-containing substance is bitumen. Bitumen, also referred toas asphalt, typically comprises polycyclic aromatic hydrocarbons. Insome embodiments, the hydrocarbon-containing substance comprises on ormore petroleum distillates. In other embodiments, thehydrocarbon-containing substance is diesel fuel. In other embodiments,the hydrocarbon-containing substance is heating oil. In otherembodiments, the hydrocarbon-containing substance is jet fuel. In otherembodiments, the hydrocarbon-containing substance is aviation gasoline.In other embodiments, the hydrocarbon-containing substance is kerosene.

In some embodiments, the methods for extracting a hydrocarbon-containingsubstance from a substrate further comprise recovering thehydrocarbon-containing substance and optionally purifying it. Forexample, where the hydrocarbon-containing substance is crude oil, theextracted crude oil can be recovered and optionally refined to provideone or more conventional oil-derived products.

In some embodiments, the hydrocarbon-containing substance is removedfrom the substrate's surface. In other embodiments,hydrocarbon-containing substance is extracted from the substrate. Insome embodiments the present methods for extracting thehydrocarbon-containing substance result in the formation of a biphasicor multiphasic mixture in which one of the phases is agglomeratedhydrocarbon-containing substance (e.g., in the form of an “oil ball”),which can be easily removed from the aqueous composition or extractantby, for example, skimming, decantation, centrifugation or filtration. Incertain embodiments, the hydrocarbon-containing substance extracted orremoved from the substrate forms one or more agglomerations that can bespherical or spheroid in shape. In some embodiments, the agglomerationsof hydrocarbon-containing material may range in diameter from about 0.1mm to about 1 cm. The size of the present agglomerations can depend onthe amount of hydrocarbon-containing substance present. Thus, where alarge amount of hydrocarbon-containing substance is present, theagglomerations may be relatively larger in diameter, ranging from about1 mm to about 10 cm or larger. In other embodiments, thehydrocarbon-containing substance does not agglomerate, but forms a layeron the top of the present aqueous compositions or extractants.

In still other embodiments, the hydrocarbon-containing substance canform “stringers,” e.g., thread-like or filamentous masses of thehydrocarbon substance that can be extracted or removed from a substrate.For example, such stringers can have a width or diameter of from about0.1 mm to about 1 cm or larger. The size of the present stringers candepend on the amount of hydrocarbon-containing substance present. Thus,where a large amount of hydrocarbon-containing substance is present, thestringers may be relatively larger in width or diameter, ranging fromabout 1 mm to about 10 cm or larger. Similarly, the stringers may have alength ranging from, e.g., about 5 mm to about 5 cm when employed inbench-scale experiments. As described with respect to width or diameterof the present stringers, that the length of the present stringers candepend on the amount of hydrocarbon-containing substance present.

In certain embodiments, the present methods further comprise subjectingthe aqueous composition, extractant or substrate to agitation. Thus, asubstrate can be contacted with the aqueous composition or extractant,and subjected to mixing, stirring, fluid circulation, or any techniqueknown in the art for agitating a mixture.

In some embodiments, the present methods can further comprise aeratingthe present aqueous compositions or extractants when admixed or combinedwith a substrate comprising a hydrocarbon-containing material. Aerationcan be effected by introducing a gas into a mixture comprising thepresent aqueous compositions or extractants and a substrate containing ahydrocarbon-containing substance. In some embodiments the gas is air. Inother embodiments, the gas is an inert gas such as carbon dioxide,nitrogen or argon. Aeration can be conducted before stirring oragitation of the mixture, concurrent with stirring or agitation, afterstirring or agitation, or any combination of before, during and afterstirring or agitation. Such aeration of the present aqueous compositionsor extractants can be effected by employing a suitable device forintroducing a gas into a fluid, e.g., a fritted glass bubble, a gasmanifold, solid or pliable tubes, etc. Gas may be introduced into themixture at a rate ranging from 0.01 L/min to about 10 L/min per liter ofaqueous composition or extractant (e.g., from about 0.01 L/min to about0.1 L/min, from about 0.1 L/min to about 0.2 L/min, from about 0.2 L/minto about 0.3 L/min, from about 0.3 L/min to about 0.4 L/min, from about0.4 L/min to about 0.5 L/min, from about 0.5 L/min to about 0.6 L/min,from about 0.6 L/min to about 0.7 L/min, from about 0.7 L/min to about0.8 L/min, from about 0.8 L/min to about 0.9 L/min, from about 0.9 L/minto about 1 L/min, from about 1 L/min to about 2 L/min, from about 2L/min to about 3 L/min, from about 3 L/min to about 4 L/min, from about4 L/min to about 5 L/min, from about 5 L/min to about 6 L/min, fromabout 6 L/min to about 7 L/min, from about 7 L/min to about 8 L/min,from about 8 L/min to about 9 L/min, from about 9 L/min to about 10L/min, or any other value or range of values therein). The amount of gasintroduced per liter of aqueous composition or extractant can depend onthe total amount of solution present and the size of the container inwhich the aqueous composition or extractant is combined with thesubstrate containing the hydrocarbon-containing substance to beextracted. Extracted hydrocarbon-containing material in the producedfroth may be separated from the froth by skimming or centrifugation. Insuch processes, hydrocarbon-containing material may be recovered from anextractant or aqueous composition after an extraction and frothingprocess, and then the extractant or aqueous composition can be recycledfor reuse in an extraction process.

Aeration of the present aqueous compositions or extractants can createfoam from the aqueous compositions or extractants. Such foams can havesufficient mechanical strength and/or stability to entrain or carryhydrocarbon-containing material which has been removed or extracted froma substrate. Thus, aeration may provide a foam which entrains andtransports an extracted hydrocarbon-containing substance out of thevessel in which such a substrate was combined with the present aqueouscompositions or extractants.

In some embodiments, the present methods for extracting ahydrocarbon-containing substance from a substrate comprise hydraulicallyfracturing the substrate with a fracturing fluid that comprises apresent aqueous composition or extractant. The method can compriseinjecting a fracturing fluid comprising a present composition orextractant into a substrate (e.g., a rock formation) at a pressureeffective to fracture the substrate. Surface pumping pressures can rangefrom about 500 psi (pounds-per-square-inch, lb/in²) to about 15,000 psi(e.g., about 500 psi, about 1,000 psi, about 1,500 psi, about 2,000 psi,about 2,500 psi, about 3,000 psi, about 3,500 psi, about 4,000 psi,about 4,500 psi, about 5,000 psi, about 5,500 psi, about 6,000 psi,about 6,500 psi, about 7,000 psi, about 7,500 psi, about 8,000 psi,about 8,500 psi, about 9,000 psi, about 9,500 psi, about 10,000 psi,about 10,500 psi, about 11,000 psi, about 11,500 psi, about 12,000 psi,about 12,500 psi, about 13,000 psi, about 13,500 psi, about 14,000 psi,about 14,500 psi, about 15,000 psi). The surface pumping pressure canvary depending on fluid injection rates, well depth and orientation(e.g., vertical, horizontal, inclined, etc.), formation type (e.g.,sandstone, limestone, etc.), perforation size and number of perforationsin the production casing across the production zone being fractured,etc. Furthermore, fluid pumping pressures typically vary over the courseof the fracturing operation, and can increase, decrease, or both duringthe course of a fracturing operation.

The fracturing fluid can further comprise one or more additives such asa proppant, viscosity modifier, radioactive tracer, gel, alcohol,detergent, acid, fluid-loss additive, gas (e.g., nitrogen or carbondioxide) dispersant or flocculant. The fracturing fluid can then berecovered or produced from the substrate (e.g., via a wellbore),extracting the hydrocarbon-containing substance from the substrate asthe fracturing fluid is recovered or produced. The resultant mixture ofthe fracturing fluid and extracted hydrocarbon-containing substance canbe further processed to separate the hydrocarbon-containing substancefrom the fracturing fluid.

Accordingly, in certain embodiments, the present invention provides ahydraulic fracturing fluid comprising an aqueous composition of thepresent invention. In certain embodiments, the hydraulic fracturingfluid further comprises an additive. In some embodiments, the additiveis one or more of a proppant, a viscosity modifier, a radioactivetracer, a gel, an alcohol, a detergent, an acid, a fluid loss additive,a gas, a dispersant or a flocculant. In other embodiments, the presentinvention provides a hydraulic fracturing fluid comprising an extractantof the present invention. In certain embodiments, the hydraulicfracturing fluid further comprises an additive. In certain embodiments,the additive is one or more of a proppant, a viscosity modifier, aradioactive tracer, a gel, an alcohol, a detergent, an acid, a fluidloss additive, a gas, a dispersant or a flocculant. In certainembodiments, the invention further provides a method for extracting ahydrocarbon-containing substance from a substrate, comprisinghydraulically fracturing the substrate with a hydraulic fracturing fluidcomprising an aqueous composition of the present invention. In otherembodiments, the present invention provides a method for extracting ahydrocarbon-containing substance from a substrate, comprisinghydraulically fracturing the substrate with a hydraulic fracturing fluidcomprising an extractant of the present invention.

The extraction efficiency, i.e., amount of hydrocarbon-containingsubstance that can be extracted from a substrate, ranges from about 5 wt% of the substrate's hydrocarbon-containing substance to 100 wt % of thesubstrate's hydrocarbon-containing substance; in one embodiment fromabout 10 wt % of the substrate's hydrocarbon-containing substance toabout 90 wt % of the substrate's hydrocarbon-containing substance; inother embodiments, at least about 5 wt %, at least about 10 wt %, atleast about 15 wt %, at least about 20 wt %, at least about 25 wt %, atleast about 30 wt %, at least about 35 wt %, at least about 40 wt %, atleast about 45 wt %, at least about 50 wt %, at least about 55 wt %, atleast about 60 wt %, at least about 65 wt %, at least about 70 wt %, atleast about 75 wt %, at least about 80 wt %, at least about 85 wt %, atleast about 90 wt %, at least about 95 wt %, at least about 96 wt %, atleast about 97 wt %, at least about 98 wt %, at least about 99 wt %,about 99.5 wt %, or greater than about 99.5 wt %, (or any other value orrange of values therein or thereabove) of the total amount ofhydrocarbon-containing substance present in or on the substrate.

In some embodiments, the present methods may be performed at ambientpressure. In other embodiments, the present methods may be conducted ata reduced pressure from about 100 mm Hg to about 760 mm Hg (e.g., fromabout 100 mm Hg to about 200 mm Hg, from about 200 mm Hg to about 300 mmHg, from about 300 mm Hg to about 400 mm Hg, from about 400 mm Hg toabout 500 mm Hg, from about 500 mm Hg to about 600 mm Hg, from about 600mm Hg to about 700 mm Hg, from about 700 mm Hg to about 760 mm Hg, orany other value or range of values therein). In other embodiments, thepresent methods may be preformed at an elevated pressure from about 760mm Hg to about 7600 mm Hg (e.g., from about 760 mm Hg to about 1520 mmHg, from about 1520 mm Hg to about 2280 mm Hg, from about 2280 mm Hg toabout 3040 mm Hg, from about 3040 mm Hg to about 3800 mm Hg, from about3800 mm Hg to about 4560 mm Hg, from about 4560 mm Hg to about 5320 mmHg, from about 5320 mm Hg to about 6080 mm Hg, from about 6080 mm Hg toabout 6840 mm Hg, from about 6840 mm Hg to about 7600 mm Hg, or anyother value or range of values therein).

The present invention further provides methods for remediating asubstrate, comprising contacting the substrate with an aqueouscomposition or extractant of the invention under conditions effectivefor remediating the substrate. As used herein, the term “remediating”includes extracting at least some hydrocarbon-containing substance froma substrate. Such hydrocarbon-containing substances and substrates arethose described above. Remediating can include purifying water such thatit becomes potable, suitable for swimming or non-toxic to aquaticspecies; converting contaminated soil to that which is useful asfarmland or for real estate; converting oil sand to sand that issuitable for commercial or recreational use, etc. Thus, remediating asubstrate can substantially improve the quality of a substrate, forexample, rendering it non-toxic. In some embodiments, remediating thesubstrate includes removing a hydrocarbon-containing substance from thesurface of a substrate, or extracting the hydrocarbon-containingsubstance from pores, fractures, cracks, fissures or crevices in asubstrate. The present methods are useful for remediatingenvironmentally contaminated sites, soils or animals.

Accordingly, in certain embodiments, the present invention providesmethods for remediating a substrate, comprising contacting the substratewith an aqueous composition of the present invention under conditionseffective for remediating the substrate. In some embodiments, thesubstrate is soil, sand, wood, paper, skin, a waterbody, gravel, mud,clay, plant, hair, fabric, glass, porcelain, concrete, metal or ananimal. In certain embodiments, the substrate is a waterbody. In otherembodiments, the substrate is soil. In some embodiments, the substrateis an animal. In some embodiments, the animal is a living animal. Inother embodiments, the animal is a dead animal. In certain embodiments,remediating comprises extracting a hydrocarbon-containing substance fromthe substrate. In other embodiments, the contacting occurs at an aqueouscomposition or a substrate temperature of about 5° C. to about 90° C.(e.g., about 5° C., about 10° C., about 15° C., about 20° C., about 25°C., about 30° C., about 35° C., about 40° C., about 45° C., about 50°C., about 55° C., about 60° C., about 65° C., about 70° C., about 75°C., about 80° C., about 85° C., about 90° C., or any other value orrange of values therein). In one embodiment, the contacting occurs at anaqueous composition or a substrate temperature of about 4° C. to about38° C. In some embodiments, the method further comprises subjecting theaqueous composition or substrate to agitation. In some embodiments, theagitation is mixing. In some embodiments, the hydrocarbon-containingsubstance is grease, oil, coal tar, bitumen, coal tar sand, sludge,oil-contaminated sludge, light tar oil or creosote. In certainembodiments, the oil is automotive oil. In other embodiments, theautomotive oil is synthetic automotive oil. In some embodiments, the oilis crude oil. In some embodiments, the hydrocarbon-containing substancecomprises one or more petroleum distillates. In other embodiments, thehydrocarbon-containing substance is diesel fuel. In other embodiments,the hydrocarbon-containing substance is heating oil. In otherembodiments, the hydrocarbon-containing substance is jet fuel. In otherembodiments, the hydrocarbon-containing substance is aviation gasoline.In other embodiments, the hydrocarbon-containing substance is kerosene.

In another aspect, the present invention provides a method forremediating a substrate, comprising contacting the substrate with anextractant of the present invention under conditions effective forremediating the substrate. In certain embodiments, the substrate issoil, sand, wood, paper, skin, a waterbody, gravel, mud, clay, plant,hair, fabric, metal or an animal. In other embodiments, the substrate isa waterbody. In some embodiments, the substrate is soil. In otherembodiments, the substrate is an animal. In some embodiments, the animalis a living animal. In other embodiments, the animal is a dead animal.In some embodiments, remediating comprises extracting ahydrocarbon-containing substance from the substrate. In certainembodiments, contacting occurs at an extractant or substrate temperatureof about 5° to about 90° C. (e.g., about 5° C., about 10° C., about 15°C., about 20° C., about 25° C., about 30° C., about 35° C., about 40°C., about 45° C., about 50° C., about 55° C., about 60° C., about 65°C., about 70° C., about 75° C., about 80° C., about 85° C., about 90°C., or any other value or range of values therein). In one embodiment,the contacting occurs at an aqueous composition or a substratetemperature of about 4° C. to about 38° C. In other embodiments, themethod further comprises subjecting the extractant or substrate toagitation. In some embodiments, the agitation is mixing. In certainembodiments, agitation comprises sonication. In other embodiments,agitation is effected by microwave. In other embodiments, thehydrocarbon-containing substance is grease, oil, coal tar, bitumen, coaltar sand, sludge, oil-contaminated sludge, light tar oil or creosote. Insome embodiments, the oil is automotive oil. In other embodiments, theautomotive oil is synthetic automotive oil. In certain embodiments, theoil is crude oil. In some embodiments, the hydrocarbon-containingsubstance comprises one or more petroleum distillates. In otherembodiments, the hydrocarbon-containing substance is diesel fuel. Inother embodiments, the hydrocarbon-containing substance is heating oil.In other embodiments, the hydrocarbon-containing substance is jet fuel.In other embodiments, the hydrocarbon-containing substance is aviationgasoline. In other embodiments, the hydrocarbon-containing substance iskerosene.

In another aspect, the present methods result in the sequestration ofhydrocarbon-containing substance present in or on the substrate. Suchmethods can comprise introducing a present aqueous composition orextractant into the soil, e.g., the soil's subsurface, via, e.g.,groundwater monitoring or one or more remediation wells. Without beingbound by any particular theory of the mechanism of such sequestration,introducing a present aqueous composition or extractant into the soilcan effectively encapsulate or agglomerate hydrocarbon-containingsubstance therein, rendering it relatively immobile. Accordingly, suchmethods can also render the hydrocarbon-containing substance effectivelyinert via sequestration.

The present methods can be performed by allowing the substrates andpresent aqueous compositions or extractants to contact within acontainer, such as a tank, vessel, pool or pit. The contacting can beperformed at atmospheric pressure or above in a batch, semi-batch orcontinuous mode, for example, where hydrocarbon-containing substance iscontinuously removed from the substrate. In some embodiments, thepresent aqueous compositions or extractants are reused after removinghydrocarbon-containing substance from a substrate or after remediating asubstrate. In other embodiments, “fresh,” previously unused aqueouscomposition or extractant is continuously contacted with the substrate.

Contacting is conducted under conditions that are effective forextracting at least some hydrocarbon-containing substance from thesubstrate or for remediating the substrate. Thus, in certainembodiments, the contacting time is about 10 minutes, about 20 minutes,about 30 minutes, about 40 minutes, about 50 minutes, about 60 minutes,about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6hours, about 12 hours, about 18 hours, about 24 hours, about two orthree days, about a week, about a month or about several months (or anyother value or range of values therein or thereabove). In addition,contacting can be conducted at a temperature of from about 5° C. toabout 90° C. (e.g., about 5° C., about 10° C., about 15° C., about 20°C., about 25° C., about 30° C., about 35° C., about 40° C., about 45°C., about 50° C., about 55° C., about 60° C., about 65° C., about 70°C., about 75° C., about 80° C., about 85° C., about 90° C., or any othervalue or range of values therein). In one embodiment, the contactingoccurs at an aqueous composition or a substrate temperature of about 4°C. to about 38° C. In one embodiment, the contacting is conducted at atemperature of from about 5° C. to about 50° C.; in other embodimentsfrom about 20° C. to about 30° C. In other embodiments the contactingoccurs at about 20° C., at about 30° C., at about 40° C., at about 50°C., at about 60° C., at about 70° C., at about 80° C., at about 90° C.,or any other value or range of values therein or thereabove).

In certain embodiments, it can be advantageous to adjust the pH of thesubstrate or the aqueous compositions or extractants, for example, toeffect a desired separation or to promote formation of aggregates ofhydrocarbon-containing substance. Thus, in certain embodiments, the pHof the substrate or the present aqueous compositions or extractants canbe adjusted to about 13, about 12, about 11, about 10, about 9, about 8,about 7, about 6, about 5, about 4, about 3 (or any other value or rangeof values therein or therebelow). Such pH adjustment can be performed byadding an acid or base as previously described herein. The acid or basecan be added continuously, or in aliquots. The acid or base can be addedundiluted or as a mixture in water or organic solvent.

Industrial extraction of oil from the Athabasca oil sands produceswastewater comprising fines, or small particulates, in the oilextraction process. These fines can remain suspended in waste water andprevent recycling of water in an extraction process, or alternatively,prevent discharge of fines-laden wastewater into the environment.Accordingly, a method to promote rapid settling of fines, therebyallowing discharge of the wastewater from an extraction process, isdesirable. Thus, in one embodiment, the present invention provides amethod for precipitating fines contained in a vessel further containinga hydrocarbon-containing material and a aqueous composition or anextractant as described herein, comprising acidifying the contents ofsaid vessel to a pH of about 4.6 or less.

Any Composition of the Invention as described herein may be employed inan extraction process which produces fines-laden water. The resultantfines-laden water, which can further comprise hydrocarbon-containingmaterial, can then be acidified to reduce the pH of the fines-ladenwater to less than about 4.6, and precipitate the fines suspendedtherein. Acids which may be suitable for reducing the pH of thefines-laden water may include organic or inorganic acids. For example,the inorganic acids may include hydrofluoric acid, hydrochloric acid,hydrobromic acid, hydroiodic acid, sulfurous acid, sulfuric acid,phosphoric acid, nitric acid and carbonic acid. Organic acids canalternatively be employed. Suitable organic acids include C₁ to C₂₀organic acids such as formic acid, citric acid, malic acid, adipic acid,tannic acid, lactic acid, ascorbic acid, acetic acid, fumaric acid, andmixtures thereof.

The acid can be added in concentrated form, or as an aqueous solution.The acid is generally added to the solution in which the fines arepresent, and can be added with concomitant agitation. Alternatively, thesolution may be agitated after addition of the acid. Such agitation mayinclude mechanical agitation, or hydraulic mixing provided by pumpingand circulation of the fines-laden fluid in the vessel in which it iscontained.

The vessel may be a metal or polymer tank, or may be an earthen pit orexcavated reservoir, which may be lined to prevent fluid communicationof the wastewater with groundwater and/or subterranean water-nearingformations. After addition of the acid, and mixing to disperse the acidin solution, the solution is typically allowed to stand for a period oftime to allow the fines to settle, and for any hydrocarbon-containingmaterial released from the fines or present in the solution to float tothe surface. Settling times may range from about 1 minute to about 1week (e.g., from about 1 minute to about 2 minutes, from about 2 minutesto about 5 minutes, from about 5 minutes to about 10 minutes, from about10 minutes to about 20 minutes, from about 20 minutes to about 30minutes, from about 30 minutes to about 40 minutes, from about 40minutes to about 50 minutes, from about 50 minutes to about 1 hour, fromabout 1 hour to about 2 hours, from about 2 hours to about 3 hours, fromabout 3 hours to about 4 hours, from about 4 hours to about 5 hours,from about 5 hours to about 6 hours, from about 6 hours to about 7hours, from about 7 hours to about 8 hours, from about 8 hours to about9 hours, from about 9 hours to about 10 hours, from about 10 hours toabout 11 hours, from about 12 hours to about 12 hours, from about 12hours to about 1 day, from about 1 day to about 2 days, from about 2days to about 3 days, from about 3 days to about 4 days, from about 4days to about 5 days, from about 5 days to about 6 days, from about 6days to about 1 week, or any other value or range of values therein).Residual hydrocarbon-containing material released during or afteracidification and/or settling can be recovered by, e.g., skimming. Inother embodiments, remaining hydrocarbon-containing material may beseparated by centrifugation. In such processes, hydrocarbon-containingmaterial may be recovered from an extractant or aqueous compositionafter an extraction process; fines can be removed by lowering the pH;and then remaining hydrocarbon-containing material can be removed bycentrifugation. The remaining extractant or aqueous composition can thenbe recycled for reuse in an extraction process.

In other embodiments, the aqueous compositions or extractants furthercomprise a substrate, which can be present in the aqueous composition orextractant in a weight ratio of substrate:aqueous composition orextractant from about 0.01:1 to about 1:1, in one embodiment, from about0.1:1 to about 1:1. However, the substrate:aqueous composition orextractant ratio is not limited, and can be selected according to aparticular application and to minimize the amount of the aqueouscomposition or extractant employed.

Thus, in certain embodiments, the present invention provides a methodfor extracting a hydrocarbon-containing substance from a substrate,comprising contacting the substrate with an aqueous composition of thepresent invention under conditions effective for extracting at leastsome of the hydrocarbon-containing substance from the substrate. Inother embodiments, the substrate is soil, sand, wood, rock, paper, skin,a waterbody, gravel, mud, clay, plant, hair, fabric, metal, glass,porcelain, concrete or an animal. In some embodiments, the substrate isa waterbody. In other embodiments, the substrate is soil. In otherembodiments, the substrate is an animal. In some embodiments, the animalis a living animal. In one embodiment, the animal is a dead animal. Inother embodiments, the extracting comprises removing thehydrocarbon-containing substance from the surface of the substrate. Insome embodiments, the contacting occurs at an aqueous composition or asubstrate temperature of about 5° to about 50° C. In other embodiments,the method further comprises subjecting the aqueous composition or thesubstrate to agitation. In one embodiment, the agitation is mixing. Incertain embodiments, agitation comprises sonication. In otherembodiments, agitation is effected by microwave. In some embodiments,the hydrocarbon-containing substance is grease, oil, coal tar, bitumen,coal tar sand, sludge, oil-contaminated sludge, light tar oil orcreosote. In other embodiments, the oil is automotive oil. In otherembodiments, automotive oil is synthetic automotive oil. In certainembodiments, the oil is crude oil. In some embodiments, thehydrocarbon-containing substance comprises one or more petroleumdistillates. In other embodiments, the hydrocarbon-containing substanceis diesel fuel. In other embodiments, the hydrocarbon-containingsubstance is heating oil. In other embodiments, thehydrocarbon-containing substance is jet fuel. In other embodiments, thehydrocarbon-containing substance is aviation gasoline. In otherembodiments, the hydrocarbon-containing substance is kerosene.

In another aspect, the present invention provides a method forextracting a hydrocarbon-containing substance from a substrate,comprising contacting the substrate with an extractant of the presentinvention under conditions effective for extracting at least some of thehydrocarbon-containing substance from the substrate. In certainembodiments, the substrate is soil, sand, wood, rock, paper, skin, awaterbody, gravel, mud, clay, plant, hair, fabric, metal or an animal.In other embodiments, the substrate is a waterbody. In some embodiments,the substrate is soil. In other embodiments, the substrate is an animal.In some embodiments, the animal is a living animal. In one embodiment,the animal is a dead animal. In certain embodiments, extractingcomprises removing the hydrocarbon-containing substance from the surfaceof the substrate. In some embodiments, contacting occurs at anextractant or a substrate temperature of about 5° to about 90° C. Insome embodiments, the method further comprises subjecting the extractantor the substrate to agitation. In certain embodiments, the agitation ismixing. In some embodiments, the hydrocarbon-containing substance isgrease, oil, coal tar, bitumen, coal tar sand, sludge, oil-contaminatedsludge, light tar oil or creosote. In other embodiments, the oil isautomotive oil. In some embodiments, the automotive oil is syntheticautomotive oil. In some embodiments, the oil is crude oil.

In another aspect the present invention provides a method for extractinga hydrocarbon-containing substance from a substrate, comprisingcontacting the substrate with an aqueous composition of the presentinvention under conditions effective for extracting at least some of thehydrocarbon-containing substance from the substrate. In someembodiments, extracting comprises removing a hydrocarbon-containingsubstance from the surface of the substrate. In other embodiments, thepresent methods for extracting hydrocarbon-containing substance from asubstrate, comprising contacting the substrate with an extractant of thepresent invention under conditions effective for extracting at leastsome of the hydrocarbon-containing substance from the substrate. Incertain embodiments, extracting comprises removing ahydrocarbon-containing substance from the surface of the substrate. Inanother embodiment, the present methods for remediating a substratecomprise contacting a substrate with an aqueous composition of thepresent invention under conditions effective for remediating thesubstrate. In some embodiments, remediating the substrate comprisessequestering one or more contaminants in the substrate. In otherembodiments, the present methods for remediating a substrate comprisecontacting the substrate with an extractant of the present inventionunder conditions effective for remediating the substrate. In someembodiments, remediating the substrate comprises sequestering one ormore contaminants in the substrate.

The following non-limiting examples illustrate various aspects of thepresent invention.

EXAMPLES Example 1

An illustrative aqueous composition of the invention comprising plantmaterial, but not comprising polysaccharide other than that present inor derived from the plant material, was prepared as follows. Citric acid(4.91 grams) was dissolved in 0.714 kg of 70% isopropanol at about 23°C. Corn gluten meal (2.28 kg) was added, and the resultant mixture wasallowed to stir for 2 hours. 2.844 kg of a 50% aqueous sodium hydroxidesolution was added to 13.6 kg of water, the resultant diluted sodiumhydroxide solution was added to the isopropanol/corn gluten mealmixture, and the resultant mixture was allowed to stand for 6 hours.Sodium chloride (9.1 g) was then added, also with stirring. Theresultant mixture was then allowed to stand an additional 2 hours.S-type hydrated lime (90.8 g) was then added with stirring, and theresultant mixture was stirred until uniform. The solids were allowed tosettle, and the supernatant was decanted to provide the illustrativeaqueous composition as the decanted supernatant.

Example 2

An illustrative aqueous composition of the invention comprising plantmaterial and polysaccharide was prepared as follows. Citric acid (4.91grams) was dissolved in 0.714 kg of 70% isopropanol at about 23° C. Corngluten meal (2.28 kg) was added, and the resultant mixture was allowedto stir for 2 hours. 2.844 kg of a 50% aqueous sodium hydroxide solutionwas added to 13.6 kg of water, the resultant diluted sodium hydroxidesolution was added to the isopropanol/corn gluten meal mixture, and theresultant mixture was allowed to stand for 6 hours. Guar gum (113.5 g)wetted with 70% isopropanol was then added to the isopropanol/corngluten meal mixture with stirring. Sodium chloride (9.1 g) was thenadded, also with stirring. The resultant mixture was then allowed tostand an additional 2 hours. S-type hydrated lime (90.8 g) was thenadded with stirring, and the resultant mixture was stirred untiluniform. The solids were allowed to settle, and the supernatant wasdecanted to provide the illustrative aqueous composition as the decantedsupernatant.

Example 3

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the resultant mixture was13.2. The mixture was then stirred using a magnetic stir bar for 135minutes at about 23° C. After 15 minutes of stirring, some extraction ofoil from the oil sand was observed. Complete extraction of the oil, asdetermined by the observation of clean sand in the bottom of the vesselafter a brief settling period, was not observed. FIGS. 1A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 1A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 1B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting at least some hydrocarbon-containing oil from asubstrate.

Example 4

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 11.1 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 2A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 2A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 2B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Example 5

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 9.1 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 3A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 3A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 3B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Example 6

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 6.9 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 4A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 4A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 4B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Example 7

In a glass vessel, the aqueous composition of Example 2 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the resultant mixture was13.2. The mixture was then stirred using a magnetic stir bar for 135minutes at about 23° C. After 15 minutes of stirring, some extraction ofoil from the oil sand was observed. Complete extraction of the oil, asdetermined by the observation of clean sand in the bottom of the vesselafter a brief settling period, was not observed. FIGS. 5A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 5A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 5B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting at least some hydrocarbon-containing oil from asubstrate.

Example 8

In a glass vessel, the aqueous composition of Example 2 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 11.1 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 6A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 6A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 6B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Example 9

In a glass vessel, the aqueous composition of Example 2 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 9.1 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 7A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 7A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 7B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Example 10

In a glass vessel, the aqueous composition of Example 2 (2.5 g) wascombined with water (47.5 g) to provide an extractant. To the extractantwas added 5 g of Athabasca oil sand. The pH of the mixture was thenadjusted to about 7 with 1M citric acid. The mixture was then stirredusing a magnetic stir bar for 135 minutes at about 23° C. After 15minutes of stirring, some extraction of oil from the oil sand wasobserved. Complete extraction of the oil, as determined by theobservation of clean sand in the bottom of the vessel after a briefsettling period, was observed after 60 min of stirring. FIGS. 8A-B arephotographs showing a side view of the mixture in the vessel after 60min of stirring then briefly allowing the mixture to settle (FIG. 8A),and a top view of the inside of the vessel after decanting thesupernatant (FIG. 8B), also after 60 min of stirring. This exampledemonstrates that an illustrative Composition of the Invention is usefulfor extracting hydrocarbon-containing oil from a substrate.

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated analogs areubiquitous environmental pollutants. They are in fossil fuels, and theirby-products can enter the environment from natural seeps or runoff fromasphalt. Incomplete combustion of organic materials can result intransporting these compounds over long distances as gaseous molecules ororganically-bound particulate matter. In addition, there are tens ofthousands of coal-tar contaminated gas plants worldwide that are andwill continue to contribute to PAH pollution.

Some PAHs are toxic, mutagenic, and carcinogenic, and therefore poserisk to human health and the environment. Alkylated PAHs have been shownto contribute substantially to the toxicity of PAH mixtures, in somecases accounting for 80% of the toxic burden. Similarly, PASHbioaccumulates and can be toxic, mutagenic, and carcinogenic.

The US EPA provides guidelines for estimating the hazards posed bycontaminated soils and sediments based on the concentration of 18 parentPAH and 16 C1 to C4 alkylated homologs. Thus, the removal and/orrecovery of PAH is of importance in the remdiation of environmentallycompromised sites and/or in the extraction of oil. The followingExamples 11 and 12 demonstrate that illustrative Compositions of theInvention are effective for removing or extracting PAH from coal tar orfrom Athabasca oil sand.

Example 11

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. Athabasca oilsand (5 g) was added to the vessel. The resultant mixture was stirredusing a magnetic stir bar for 4 hr at about 23° C., and an oil ball wasformed. The PAH content of the oil sand was measured by GC-MS before andafter extraction, to determine the extractant's extraction efficiency.PAHs whose concentration was detected include naphthalene, fluorene,phenanthrene, pyrene, chrysene, and C₁-C₄ homologs thereof. A C₁ homologof a PAH is a PAH having a methyl group. A C₂ homolog of a PAH is a PAHhaving, for example, an ethyl group or two methyl groups. A C₃ homologof a PAH is a PAH having, for example, a methyl and an ethyl group,three methyl groups, an n-propyl group or an i-propyl group. A C₄homolog of a PAH is a PAH having, for example, two ethyl groups, fourmethyl groups, an ethyl group and two methyl groups, a methyl group andan n-propyl group, a methyl group and an i-propyl group, an n-butylgroup, a sec-butyl group, and i-butyl group or a t-butyl group. Theresults of these analyses are shown in Table 1 below:

TABLE 1 PAH Concentrations in Oil Sand Before and After Extraction (μgPAH/g Sand) PAH Before Extraction (μg/g) After Extraction (μg/g)Naphthalene not detected not detected C₁ homolog not detected notdetected C₂ homolog not detected not detected C₃ homolog not detectednot detected C₄ homolog not detected not detected Fluorene not detectednot detected C₁ homolog 3.3 not detected C₂ homolog not detected notdetected C₃ homolog not detected not detected C₄ homolog not detectednot detected Phenanthrene 3.6 not detected C₁ homolog 24.1  0.4 C₂homolog 38.9  0.6 C₃ homolog 47.2  0.7 C₄ homolog 7.7 not detectedPyrene 5.6 not detected C₁ homolog 2.1 not detected C₂ homolog notdetected not detected C₃ homolog not detected not detected C₄ homolognot detected not detected Chrysene 2.7 not detected C₁ homolog 9.0 notdetected C₂ homolog 9.2 not detected C₃ homolog not detected notdetected C₄ homolog not detected not detected

This example demonstrates that an illustrative Composition of theInvention is useful for extracting PAH-containing oil from a substrate.

Based on the low PAH content of the Athabasca oil sand, as shown inExample 11 above, relative to coal tar, as shown in Example 12, below,it was important to confirm for a larger group of PAH if the percentreduction in PAH content is characteristic of the present extractionmethods employing Compositins of the Invention. Thus, a coal tar sandwas extracted as described in Example 12, below.

Example 12

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. Coal tar sandfrom a North Carolina gasification plant site (5 g, 15 wt % coal tar)was added to the extractant. The resultant mixture was stirred using amagnetic stir bar for 90 minutes at about 23° C. Extraction of the coaltar from the sand was observed after 10 minutes, and a ball of coal tarwas observed at 90 minutes. The polycyclic aromatic hydrocarbon (PAH)content of the coal tar sand was measured by GC-MS before and afterabove-described extraction to determine the extractant's extractionefficiency. The results of these analyses are shown in Table 2 below:

TABLE 2 PAH Concentrations in Coal Tar Sand Before and After Extraction(mg PAH/kg) Sand) Before After PAH Extraction Extraction % ExtractionAcenaphthene 1.3 0.0 100 Acenaphthylene 392.4 7.4 98.1 Anthracene 418.88.5 98.0 benz[a]anthracene 299.9 6.7 97.8 benzo[a]pyrene 216.1 4.8 97.8Benzo[b]fluoranthene 103.9 2.6 97.5 benzo[ghi]perylene 77.1 1.7 97.9benzo[k]fluoranthene 126.6 2.6 98.0 Chrysene 299.3 6.8 97.7dibenz[ah]anthracene 23.2 0.4 98.1 Fluoranthene 712.5 11.7 98.4 Fluorene419.5 8.3 98.0 Indeno[1,2,3-cd]pyrene 79.9 1.5 98.1 Naphthalene 502.58.1 98.4 Phenanthrene 1444.5 31.4 97.8 Pyrene 853.2 15.1 98.2

This example demonstrates that an illustrative Composition of theInvention is useful for extracting PAH-containing coal tar from asubstrate.

The percent decrease in PAH content in the tar sand as shown in Example12, above, was consistent from homolog to homolog. Since theconcentration of the various PAHs measured decreases in similar amounts,these data indicate that the extractant removes PAH from the coal tarsand without selectivity.

Example 13

Athabasca oil sand (5 g) was added to a 100 ml glass beaker. Anextractant of a mixture of the aqueous composition of Example 1 (2.5 g)in water (47.5 g) was added to the Athabasca oil sand (5 g) at about 23°C. FIGS. 9 and 10 are photographs showing a top-down (FIG. 9) and side(FIG. 10) view of the contents in the beaker before stirring (see alsowhite magnetic stir bar in photograph). Evident in FIGS. 9 and 10 is thelumpiness of the oil sands, and that the sand is completely surroundedby oil. Also shown are air bubbles, produced upon addition of theextractant to the oil sands. In contrast, no bubbles appeared whenpouring merely water over the oil sands or when pouring the extractantinto an empty beaker. The extractant was yellow in color.

The mixture of extractant and oil sand was then stirred. FIG. 11 is aphotograph showing the contents of the beaker after stirring for 4 min,then allowing most of the solids to settle. FIG. 11 shows stringers ofoil separating from sand. This result is consistent with conventional,elevated temperature, water-based oil sand extraction processes. FIG. 11shows separation occurring at room temperature within the same 5 minutetimeframe as in current conventional, elevated temperature, water-basedoil sand extraction processes. Evident is the change in color of thesolution and the appearance of loosely scattered “free” oil and sandparticles from the lumpy oil sands. As particles settle, oil-containingsands sit on top of “cleaner” sand as it is beginning to separate fromthe lumpier oil sands.

FIG. 12 is a photograph showing the contents of the beaker afterstirring for 10 minutes. Evident are longer stringers of “free” oilseparated from the sands. Conversely, FIG. 13 is a photograph showingsand “free” of oil that has settled to the bottom of the beaker a fewminutes after stirring was stopped. FIG. 14 is a photograph showing theagglomerating oil deposits sitting on top of the sand after decantingthe solution into another beaker.

FIGS. 15-16 are photographs showing the contents of the beaker afterstirring 30 minutes and then decanting the solution into a secondbeaker. FIG. 15 is a photograph of “free” oil sticking to the glass ofthe beaker in which the oil sand and extractant were stirred, afterdecanting the extractant liquid comprising some extracted oil into asecond beaker. FIG. 16 is a photograph showing the remaining sand andoil in the beaker in which the oil sand and extractant were stirredafter decanting the extractant liquid comprising some extracted oil intothe second beaker. As shown in FIG. 16, the remaining oil in the bottomof the beaker begins to pool as a dense, non-aqueous phase liquid(DNAPL), which, for the most part, has separated from the sand.

FIG. 17 is a photograph showing the sand, oil and magnetic stir barremaining in the beaker after stirring for 1 hour and decanting theresultant supernatant. FIG. 18 is a photograph showing the oil remainingon the glass of the first beaker after transferring the sand, oil andextractant to a second beaker.

This example demonstrates that an illustrative Composition of theInvention is useful for extracting oil from Athabasca oil sands.

Example 14

Athabasca oil sand (5 g comprising 15±6 wt % oil and 83±6% sand) wascombined with 50 mL of toluene and stirred at about 23° C. This tolueneextraction was repeated seven times for each 5 g sample of Athabasca oilsand. The extractions were performed in triplicate (i.e., threedifferent samples). A total of 2% of the mass of the oil sand was lostduring separation of “free” oil from sand. As reported below, mass ofoil (wt %) or mass of sand (wt %) are reported as the mass percent ofeach versus the total sample weight (i.e., mass of oil=oil extractedfrom Athabasca oil sand (g)/total mass of original Athabasca oil sandsample (g)×100; mass of sand=mass of sand remaining after extraction(g)/mass of original Athabasca oil sand sample (g)×100). Variation amongthe three extractions is reported as RSD (relative standard deviation).A summary of these analyses is shown below in Table 3:

TABLE 3 Mass Percent Oil and Sand in Athabasca Oil Sand by SolventExtraction Extraction 1 Extraction 2 Extraction 3 Mass of Oil (wt %) 16%16% 14% Mass of Sand (wt %) 84% 82% 84% Average Mass of Oil 15% AverageMass of Sand 83% (wt %) (wt %) RSD 6% RSD 1%

The Athabasca oil sand was also analyzed by Alberta Innovates—TechnologyFutures of Canada to determine its total oil, water and solids content,as shown below in Table 4:

TABLE 4 Mass Percent Oil, Water and Solids and Sand in Athabasca OilSand by Solvent Extraction Total Athabasca Total Mass Total Oil SandRecovered Oil Water Solids Oil Water Solids Recovery (grams) (grams)(grams) (grams) (grams) (wt %) (wt %) (wt %) (%) 87.03 86.18 10.68 1.0074.50 12.27 1.15 85.6 99.02

In a glass vessel, the aqueous composition of Example 1 (2.5 g) wascombined with water (47.5 g) to provide an extractant. Athabasca oilsand (5 g) was added to the extractant. The mixture of oil sand andextractant was stirred using a magnetic stir bar for 4 hr at about 23°C. Oil recovery extraction efficiency after 4 hr stirring, based ontotal oil present in the Athabasca oil sand, was 84±10 wt % based on theoil sand composition as shown in Table 3, above. However, if the oilsand composition data from the analyses performed by AlbertaInnovates—Technology Futures of Canada in Table 4 above are used as thebaseline for oil content in the oil sands, the extraction efficiency ofan illustrative Composition of the Invention approaches 100%. Thesefindings are impressive when contrasted with commercial recoveries of80-95 wt % of oil from oil sands given that the present illustrativeComposition of the Invention was employed at room temperature, whereascommercial extractions processes operate between 35° C. and 80° C. andneed surfactants, steam, and air.

The particle-size distribution of the solids in the Athabasca oil sandswas also determined (FIG. 19). The values from the particle sizedistribution analysis FIG. 19 were as follows:

Volume Statistics (Arithmetic) Calculations from 0.375 μm to 2000 μmVolume: 100% Mean: 121.8 μm S.D.:  59.13 μm Median: 127.9 μm Variance:  3496 μm² Mean/Median ratio: 0.953 C.V.: 48.5% Mode: 153.8 μm Skewness:−0.365 Left skewed Kurtosis: −0.462 Platykurtic d₁₀: 24.59 μm d₅₀: 127.9μm d₉₀: 194.4 μm <10% <25% <50% <75% <90% 24.59 μm 87.78 μm 127.9 μm164.1 μm 194.4 μm

In summary, these findings show that an illustrative Composition of theInvention can provide at least as efficient extraction of oil fromAthabasca oil sand relative to conventional, elevated temperature,water-based oil sand extraction processes.

Example 15

Athabasca oil sand (5 g) was combined with water (50 g) and stirred 4 hrat room temperature. The resultant mixture did not comprise aComposition of the Invention.

No extraction of oil from the oil sand was observed.

Example 16

To quantify the amount of protein present in illustrative aqueouscompositions of the invention, a Biuret assay was employed. Each aqueouscomposition described in Table 5, below, was assayed to determine totalprotein concentration in parts per thousand (ppt). In each experiment, afirst solution was prepared by dissolving 3.46 g of cupric sulfate in 20mL of 50° C. water. A second solution was prepared by dissolving 34.6 gof sodium citrate and 20.0 g of sodium carbonate in 80 mL of 50° C.water. After allowing the first and second solutions to cool to 23° C.,the first and second solutions were combined and mixed, yielding theBiuret assay reagent. Commercially sourced zein was dissolved in 70%isopropanol, and a calibration curve using various concentrations ofzein was constructed. To measure the concentration of protein in thevarious aqueous compositions listed in Table 5, comprising as defined inExample 24 below, one mL of the aqueous composition was admixed with 1ml of a 6 parts:100 (weight/weight) sodium hydroxide solution. To thismixture was added 0.4 mL of the Biuret assay reagent; providing a totalvolume was 2.4 mL. The test mixture's absorbance was measured at 545 nmin a 1 cm polystyrene cuvette after approximately 90 minutes. Theabsorbance was correlated to the calibration curve to provide proteinconcentration in the test mixture in parts per thousand. The results ofthe Biuret assay experiments are shown below:

TABLE 5 Protein concentration of Illustrative Aqueous Compositions asDetermined via Biuret Assay. Mass of Protein Aqueous Protein Mass ofNaOH Protein Concentration Composition Source (g) Source (g) (ppt) 4.1Corn 15.9 39.8 53.4 Gluten Meal 10.2.1 Corn 15.9 19.9 41.3 Gluten Meal12.2.6 Wheat 45.0 19.9 35.4 Germ 12.2.2 Wheat 30.0 19.9 30.0 Germ 12.1.6Wheat 45.0 19.9 32.5 Germ 13.2.4 Flax Seed 15.9 19.9 21.1 Meal 2.1.7Corn 15.9 19.9 23.0 Gluten Meal 13.2.3 Flax Seed 45.0 19.9 15.5 Meal

Example 17

Approximately 5 ml of light tar oil obtained from an industrial oilstorage tank in New Jersey (light tar oil is an oil having a viscositysimilar to room-temperature honey or syrup, which is less dense thanwater, and is pourable) was introduced into each of two glass beakers.The light tar oil, while less dense than water, adhered to the bottom ofthe glass beaker. To the first beaker was added approximately 50 ml ofwater (labeled “water”). To the second beaker was added approximately 50ml of a solution comprising 5 parts of the composition of Example 1 and95 parts water by weight (labeled “Example 1”).

FIG. 20 is a series of photographs showing the effects of a solutioncomprising 5 parts of the composition of Example 1 and 95 parts water byweight versus water on light tar oil. The first photograph, on the farleft, shows the light tar oil in the bottom of a glass beaker before theaddition of either water or a Composition of the Invention. The top rowof photographs is a time-lapse set of images showing the effects ofadding water to light tar oil as described. Although the mechanicaleffect of pouring water spreads the light tar oil apart, it does notdisperse the light tar oil in solution. As shown in FIG. 20, stirringwith a glass pipette does not disperse the light tar oil; instead thelight tar oil sticks to the beaker and the pipette. After vigorousstirring with the pipette, only small balls of light tar oil are formed,which eventually float to the surface.

In contrast, the bottom row of photographs in FIG. 20 illustrates theeffect of a solution comprising 5 parts of the composition of Example 1and 95 parts water by weight on the light tar oil. Immediately uponaddition, “stringers” of light tar oil begin to from the tar oil and arereleased from the mass of tar oil adhering to the bottom of the beaker.Stirring the mixture with a glass pipette, as shown, releases morestringers, and the mixture becomes dark with the amount of releasedlight tar oil. After allowing the mixture to stand for approximately 20seconds, the light tar oil begins to float to the top of the mixture.This experiment illustrates the ability of a Composition of theInvention to remove light tar oil from a substrate.

Example 18

Approximately 5 ml of coal tar obtained from a utility plant in NorthCarolina was introduced into each of two glass beakers. The coal taradhered to the bottom of the glass beaker. To the first beaker was addedapproximately 50 ml of water (labeled “water”). To the second beaker wasadded approximately 50 ml of a solution comprising 5 parts of thecomposition of Example 1 and 95 parts water by weight (labeled “Ex. 1”).

FIG. 21 is a series of photographs showing the effects of a solutioncomprising 5 parts of the composition of Example 1 and 95 parts water byweight versus water on coal tar. The first photograph, on the far left,shows the coal tar in the bottom of a glass beaker before the additionof either water or a Composition of the Invention. The top row ofphotographs is a time-lapse set of images showing the effects of addingwater to coal tar as described. The mechanical effect of pouring wateron coal tar does not disperse any of the coal tar in solution. As shown,stirring with a glass pipette also does not disperse the coal tar;instead the coal tar sticks to the beaker and the pipette. Aftervigorous stirring with the pipette, no coal tar is released from themass adhered to the bottom of the beaker.

In contrast, the bottom row of photographs in FIG. 21 illustrates theeffect of a solution comprising 5 parts of the composition of Example 1and 95 parts water by weight on the coal tar. Upon stirring, the coaltar forms stringers in solution. The solution darkens with increasedstirring, as more coal tar is liberated from the mass of coal taradhered to the bottom of the beaker. Upon standing, the coal tar formsballs, which sink to the bottom of the beaker. This experimentillustrates the ability of a Composition of the Invention to remove coaltar from a substrate.

Example 19

Approximately 10 ml of oil-contaminated sludge, comprising sediment andoil, was introduced into each of two glass beakers. To the first beakerwas added approximately 50 ml of water (labeled “water”). To the secondbeaker was added approximately 50 ml of a solution comprising 5 parts ofthe composition of Example 1 and 95 parts water by weight (labeled “Ex.1”).

FIG. 22 is a series of photographs showing the effects of a solutioncomprising 5 parts of the composition of Example 1 and 95 parts water byweight versus water on oil-contaminated sludge. The first photograph, onthe far left, shows the oil-contaminated sludge in the bottom of a glassbeaker before the addition of either water or a Composition of theInvention. The top row of photographs is a time-lapse set of imagesshowing the effects of adding water to oil-contaminated sludge asdescribed. The mechanical effect of pouring water on theoil-contaminated sludge breaks up the sludge slightly, but even withsubsequent stirring, the majority of the oil-contaminated sludge remainsadhered to the bottom of the beaker and the oil from theoil-contaminated sludge does not disperse in the solution. As shown,stirring with a glass pipette does not disperse the oil in theoil-contaminated sludge.

In contrast, the bottom row of photographs in FIG. 22 illustrates theeffect of a solution comprising 5 parts of the composition of Example 1and 95 parts water by weight on the oil-contaminated sludge. Uponstirring, the solution darkens, and oil is liberated from theoil-contaminated sludge. This experiment illustrates the ability of aComposition of the Invention to remove oil from oil-contaminated sludge.

Example 20

Athabasca oil sand (5 g) was added to a 100 ml glass beaker. 50 ml of anextractant made by admixing the aqueous composition of Example 1 (2.5 g)and water (47.5 g) was added to the Athabasca oil sand at about 23° C.The resultant mixture was stirred for 2 hrs. After stirring and allowingthe solids to settle, the mixture was decanted and the extracted oil andsand were separated, then dried and weighed to determine recovery ofoil. The supernatant recovered after stirring was reserved. A secondsample of Athabasca oil sand and clean stir bar was added to a cleanbeaker, the reserved supernatant was added to the beaker, and theresultant mixture was stirred at 1000 rpm for 2 hours with a magneticstir bar. This extraction, recovery, and re-use of the reservedsupernatant was repeated for a total of 6 extraction iterations. Table6, below, reports the percent of oil recovered, where the reservedsupernatant is re-used for multiple sequential extractions of separatesamples of Athabasca oil sands.

TABLE 6 Recovery of oil when extractant is used iteratively. Trial 1Trial 2 Trial 3 Trial 4 Trial 5 Trial 6 wt % of oil 90% 89% 86% 99% 93%106% recovered Average 94% RSD 8%

As can be seen from the results presented in Table 6 above, the totalrecovery of oil from each 5 g sample of Athabasca oil sand does notchange within error over successive extractions with the sameextractant. This experiment illustrates the ability of a Composition ofthe Invention to be reused to remove oil from Athabasca oil sands.

Example 21

Approximately 5 g of Athabasca oil sand (containing 15 wt % oil), 50 mlof a solution comprising 5 parts of the composition of Example 1 and 95parts water by weight, and a stir bar were added to a small glass beakerand stirred for 10 minutes. The small beaker was placed inside a largerbeaker, and the mixture in the small beaker was aerated by introducingair into the mixture via a fritted glass bubbler at 0.15 L/min for 10min. The aeration formed an oil-entrained froth which spilled over thesides of the small beaker into the larger beaker. The froth and oil inthe larger beaker, and the sand and oil remaining in the small beaker,were each separately collected, dried, and then extracted with a 50/50(v/v) mixture of toluene and dichloromethane. After removal of thetoluene/dichloromethane solvent mixture under vacuum, the percent massof oil recovered from each of the small and larger beakers wascalculated to determine the amount of oil carried from the small beakerto the larger beaker by the froth generated during aeration. FIG. 23 isa process flow diagram illustrating the process employed for frothingand extracting oil from Athabasca oils sands. Forty-three wt % of theoil present in the 5 g of Athabasca oil sand was found to have beentransported from the small beaker to the larger beaker by the frothgenerated during aeration. This amount is significant. Unlike theindustrial process described hereinabove, wherein oil sands are treated(e.g., stirred with high pH water and aerated) multiple times to removeoil therefrom, the present 43 wt % recovery was effected in a singleaeration step. This example illustrates the ability of a Composition ofthe Invention to remove oil from Athabasca oil sand using aeration.

FIG. 24 is a series of photographs from three aeration experimentsperformed as described above, but without recovery and quantification ofoil in the small and larger beakers, to qualitatively assess thefrothing properties of the present Compositions of the Invention whenaerated. The experiments employed (i) a solution comprising 5 parts ofthe composition of Example 1 and 95 parts water by weight (labeled “Ex.1”), (ii) a solution comprising 5 parts of composition 2.2.8 (asdescribed in Example 24 below) and 95 parts water by weight (labeled“2.2.8”), and (iii) a solution comprising 5 parts of composition 8.1 (asdescribed in Example 24 below) and 95 parts water by weight (labeled“8.1”). All three photographs in FIG. 25 show froth with entrained oilbeing carried out of the small beaker and into the larger beaker. Thisexample illustrates the ability of Compositions of the Invention toremove oil from Athabasca oil sand with aeration.

Example 22

Approximately 5 g of coal tar sand was placed in a glass beaker. 50 mlof an extractant made by admixing the aqueous composition of Example 1(2.5 g) and water (47.5 g) was added to the beaker at about 23° C. Theresultant mixture was stirred for 2 hours, then aerated for 10 minutesas described in Example 21. FIG. 25 is a series of two photographsillustrating the results. Coal tar from the coal tar sand is initiallycarried out with the froth, but its lower portion contains little or nocoal tar (see photograph on the left in FIG. 25). After brieflyagitating the sand and coal tar at the bottom of the beaker duringaeration of the mixture, additional coal tar was carried out by thefroth produced during aeration (see photograph on the right in FIG. 25).This example illustrates the ability of a Composition of the Inventionto remove coal tar from coal tar sand with aeration.

Example 23

FIG. 26 is a series of photographs showing the settling effect onsuspended fines by reducing the pH of a solution comprising 5 parts ofthe composition of Example 1 and 95 parts water by weight, afterextraction and removal of extracted oil from a 5 g sample of Athabascaoil sand. Athabasca oil sand (5 g) was added to a 100 ml glass beaker.50 ml of an extractant made by admixing the aqueous composition ofExample 1 (2.5 g) and water (47.5 g) was added to the Athabasca oil sandat about 23° C. The resultant mixture was stirred for 2 hrs. Afterstirring, the mixture was decanted, extracted oil and sand were removedfrom the decanted mixture, and the remaining mixture, comprisingsuspended fines, was placed in a 100 ml glass beaker, was then acidifiedfrom pH 13 to pH 4.7. The pH of the mixture was then adjusted to 4.6,and as shown in FIG. 26, the fines in the mixture were precipitated overa 160 second time period. In addition, residual oil in the mixture wasobserved to rise to the top of the mixture concurrent with the observedprecipitation of fines. This example illustrates that acidification of aComposition of the Invention, after extraction and removal of oil fromAthabasca oil sand, can effect precipitation of fines.

Example 24

A series of Experiments was performed to evaluate illustrativecompositions of the invention prepared using various plant sources, andto assess the effect of various components in Compositions of theInvention. Each composition was prepared by the method described inExperiment 1, then 5 parts by weight of it were admixed with 95 parts byweight of water to provide a solution of the composition to be tested.The contents of each composition are described in Tables 7-18, below.All experiments employed the method for extracting light tar oil asdescribed in Example 17, using the light tar oil described therein.

Experiment Series 1

Experiment series 1 was performed as shown in Table 7, employing corngluten meal as the plant source.

TABLE 7 Results of Experiment Series 1 Plant 50% S-type Source NaOH H₂Ohydrated Expt. # (g) (g) (mL) NaCl (g) lime (g) 1.2 39.8 15.89 237.80.159 0 1.3 39.8 15.89 237.8 0 1.58 1.4 39.8 15.89 237.8 0.159 1.58

The compositions of Table 7 successfully released light tar oil from themass of tar oil adhering to the bottom of the beaker. These experimentsillustrate that Compositions of the Invention are effective in removingoil from a substrate.

Experiment Series 2.1

Experiment series 2.1 was performed as shown in Table 8, employing corngluten meal at the protein source at a reduced concentration relative tothe composition of Example 1.

TABLE 8 Results of Experiment Series 2.1 Plant Citric 70% 50% S-typeExpt. Source Acid isopropanol NaOH H₂O NaCl hydrated # (g) (g) (mL) (g)(mL) (g) lime (g) 2.1.1 19.9 0.086 15.89 15.89 237.8 0.159 1.58 2.1.319.9 0 0 15.89 237.8 0.159 0 2.1.4 19.9 0 0 15.89 237.8 0 1.58 2.1.519.9 0 0 15.89 237.8 0.159 1.58 2.1.6 19.9 0.086 15.89 15.89 237.8 0 02.1.7 19.9 0.086 15.89 15.89 237.8 0 1.58 2.1.8 19.9 0.086 15.89 15.89237.8 0.159 0

The compositions of Table 8 successfully released light tar oil from themass of tar oil adhering to the bottom of the beaker. These experimentsillustrate that Compositions of the Invention are effective in removingoil from a substrate.

Experiment Series 2.2

Experiment series 2.2 was performed as shown in Table 9, employing corngluten meal at the protein source at a reduced concentration relative tothe composition of Example 1.

TABLE 9 Results of Experiment Series 2.2 Plant Citric 70% 50% S-typeExpt. Source Acid isopropanol NaOH H₂O NaCl hydrated # (g) (g) (mL) (g)(mL) (g) lime (g) 2.2.1 9.95 0.086 15.89 15.89 237.8 0.159 1.58 2.2.39.95 0 0 15.89 237.8 0.159 0 2.2.4 9.95 0 0 15.89 237.8 0 1.58 2.2.59.95 0 0 15.89 237.8 0.159 1.58 2.2.6 9.95 0.086 15.89 15.89 237.8 0 02.2.7 9.95 0.086 15.89 15.89 237.8 0 1.58 2.2.8 9.95 0.086 15.89 15.89237.8 0.159 0

The compositions of Table 9 successfully released light tar oil from themass of tar oil adhering to the bottom of the beaker. These experimentsillustrate that Compositions of the Invention are effective in removingoil from a substrate.

Experiment Series 2.3

Experiment series 2.3 was performed as shown in Table 10, employing corngluten meal at the protein source at a reduced concentration relative tothe composition of Example 1.

TABLE 10 Results of Experiment Series 2.3 Plant Citric 70% 50% S-typeExpt. Source Acid isopropanol NaOH H₂O NaCl hydrated # (g) (g) (mL) (g)(mL) (g) lime (g) 2.3.3 4.98 0 0 15.89 237.8 0.159 0 2.3.4 4.98 0 015.89 237.8 0 1.58 2.3.8 4.98 0.086 15.89 15.89 237.8 0.159 0

The compositions of Table 10 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 4

Experiment series 4 was performed as shown in Table 11, employing corngluten meal as the plant source with added polysaccharide.

TABLE 11 Results of Experiment Series 4 Plant 70% 50% S-type SourceCitric isopropanol NaOH H₂O Guar hydrated Expt. # (g) Acid (g) (mL) (g)(mL) Gum (g) NaCl (g) lime (g) 4.1 39.8 0.086 15.89 15.89 237.8 1.9780.159 1.58 4.2 39.8 0 0 15.89 237.8 1.978 0 0 4.3 39.8 0 0 15.89 237.81.978 0.159 0 4.4 39.8 0 0 15.89 237.8 1.978 0 1.58 4.5 39.8 0 0 15.89237.8 1.978 0.159 1.58 4.6 39.8 0.086 15.89 15.89 237.8 1.978 0 0 4.739.8 0.086 15.89 15.89 237.8 1.978 0 1.58 4.8 39.8 0.086 15.89 15.89237.8 1.978 0.159 0

The compositions of Table 11 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 4b

Experiment series 4b was performed as shown in Table 12, employingcotton seed meal as the plant source with added polysaccharide.

TABLE 12 Results of Experiment Series 4b Plant 70% 50% S-type SourceCitric isopropanol NaOH H₂O Guar hydrated Expt. # (g) Acid (g) (mL) (g)(mL) Gum (g) NaCl (g) lime (g) 4b.1 19.9 0.086 15.89 15.89 237.8 1.9780.159 1.58 4b.2 19.9 0 0 15.89 237.8 1.978 0 0 4b.3 19.9 0 0 15.89 237.81.978 0.159 0 4b.4 19.9 0 0 15.89 237.8 1.978 0 1.58 4b.5 19.9 0 0 15.89237.8 1.978 0.159 1.58 4b.6 19.9 0 0 15.89 237.8 1.978 0 0 4b.8 19.9 0 015.89 237.8 1.978 0.159 0

The compositions of Table 12 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 6

Experiment series 6 was performed as shown in Table 13, employing wheatgerm as the plant source.

TABLE 13 Results of Experiment Series 6 Plant Citric 50% Guar S-typeSource Acid 70% isopropanol NaOH H₂O Gum NaCl hydrated Expt. # (g) (g)(mL) (g) (mL) (g) (g) lime (g) 6.1 39.8 0.086 15.89 15.89 237.8 1.9780.159 1.58

The compositions of Table 13 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 7

Experiment series 7 was performed as shown in Table 14, employing flaxseed as the plant source.

TABLE 14 Results of Experiment Series 7 Plant Citric 50% Guar S-typeSource Acid 70% isopropanol NaOH H₂O Gum NaCl hydrated Expt. # (g) (g)(mL) (g) (mL) (g) (g) lime (g) 7.1 19.9 0.086 15.89 15.89 237.8 1.9780.159 1.58

The compositions of Table 14 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 8

Experiment series 8 was performed as shown in Table 15, employing cottonseed meal in varying amounts as the plant source.

TABLE 15 Results of Experiment Series 8 Plant Citric 70% 50% S-typeExpt. Source Acid isopropanol NaOH H₂O NaCl hydrated # (g) (g) (mL) (g)(mL) (g) lime (g) 8.1 19.9 0.086 15.89 15.89 237.8 0.159 0 8.2 9.950.086 15.89 15.89 237.8 0.159 0 8.3 4.975 0.086 15.89 15.89 237.8 0.1590 8.4 19.9 0.086 15.89 15.89 237.8 0.159 1.58 8.5 9.95 0.086 15.89 15.89237.8 0.159 1.58 8.6 4.975 0.086 15.89 15.89 237.8 0.159 1.58

The compositions of Table 15 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 10.2

Experiment series 10.2 was performed as shown in Table 16, employingcorn gluten meal as the plant source, various concentration of base(sodium hydroxide), and corn gluten meal is either soaked in water for12 hours prior to use (Expts. 10.2.1-10.2.3) or the used dry (Expts.10.2.4-10.2.6).

TABLE 16 Results of Experiment Series 10.2 Plant 50% Source NaOH H₂OExpt. # (g) (g) (mL) NaCl (g) 10.2.1 19.9 15.89 253.69 0.159 10.2.2 19.930 253.69 0.159 10.2.3 19.9 45 253.69 0.159 10.2.4 19.9 15.89 253.690.159 10.2.5 19.9 30 253.69 0.159 10.2.6 19.9 45 253.69 0.159

The compositions of Table 16 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 12.2

Experiment series 12.2 was performed as shown in Table 17, employingwheat germ as the plant source, various concentration of base (sodiumhydroxide), and the wheat germ is either soaked in water for 12 hoursprior to use (Expts. 12.2.1-12.2.3) or used dry (Expts. 12.2.4-12.2.6).

TABLE 17 Results of Experiment Series 12.2 Plant 50% Source NaOH H2OExpt. # (g) (g) (mL) NaCl (g) 12.2.1 19.9 15.89 253.69 0.159 12.2.2 19.930 253.69 0.159 12.2.3 19.9 45 253.69 0.159 12.2.4 19.9 15.89 253.690.159 12.2.5 19.9 30 253.69 0.159 12.2.6 19.9 45 253.69 0.159

The compositions of Table 17 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Experiment Series 13.2

Experiment series 13.2 was performed as shown in Table 18, employingflax seed meal as the plant source, various concentration of base(sodium hydroxide), and the flax seed is either soaked in water for 12hours prior to use (Expts. 13.2.1-13.2.3) or used dry (Expts.13.2.4-13.2.6).

TABLE 18 Results of Experiment Series 13.2 Plant 50% Source NaOH H2OExpt. # (g) (g) (mL) NaCl (g) 13.2.1 19.9 15.89 253.69 0.159 13.2.2 19.930 253.69 0.159 13.2.3 19.9 45 253.69 0.159 13.2.4 19.9 15.89 253.690.159 13.2.5 19.9 30 253.69 0.159 13.2.6 19.9 45 253.69 0.159

The compositions of Table 18 successfully released light tar oil fromthe mass of tar oil adhering to the bottom of the beaker. Theseexperiments illustrate that Compositions of the Invention are effectivein removing oil from a substrate.

Example 25

Compositions 10.2.1 and 12.2.6 as described in Example 24, above, werelyophilized, either before centrifugation, or after centrifugation toremove solids and gel formed during preparation. In addition, theComposition of Example 2 was lyophilized after its preparation by themethod below.

Lyophilization was performed by placing each composition in a 50 mLloosely covered plastic vial, immersing the vial in liquid nitrogen for30 min, then placing the vial in a bench-top manifold freeze dryer andapplying vacuum (approximately 10⁻² torr) for 48 hours. The compositionswere weighed before and after lyphilization. The amount of liquidremoved was determine by the difference between the initial mass of thecomposition prior to lyophilization and its mass after lyophilization.The results are reported in Table 19, below.

TABLE 19 Mass of Solids Recovered and Liquid Removed in Centrifugationof Exemplary Compositions of the Invention Mass of Solids Mass of LiquidExpt. # (g) Removed (g) 10.2.1 - Centrifuged 2.704 20.921 10.2.1 -Non-centrifuged 2.723 21.307 12.2.6 - Centrifuged 2.723 11.395 12.2.6 -Non-centrifuged 5.497 21.647 Example 2 - Centrifuged 3.492 21.139

The recovered solids from each composition were reconstituted withwater. Reconstitution was performed in each of two ways: 1) adding waterto provide a solution having a concentration equal to 5 parts of thecomposition prior to lyophilization and 95 parts water; and 2) byreconstituting the solids to provide a mixture having the same mass asthe composition prior to lyophilization, then admixing 5 parts of thereconstituted mixture and 95 parts water. No observable differences wereobserved in preparing the compositions using the two reconstitutionmethods.

The efficacy of the reconstituted materials for extraction of light taroil, extraction of coal tar, and frothing and extraction of Athabascasand was assessed using methods described hereinabove. The compositionswere observed to perform essentially the same as comparable,non-lyophilized, non-reconstituted counterparts in each experiment.

These experiments illustrate that lyophilized and reconstitutedCompositions of the Invention are effective for removing oil from asubstrate, for extracting coal tar from coal tar sands, and for removingoil from Athabasca oil sand using frothing.

Example 26

An illustrative aqueous composition of the invention comprising plantmaterial, but not comprising polysaccharide other than that present inor derived from the plant material, was prepared as follows. Citric acid(0.086 grams) was dissolved in 15.89 ml of 70% isopropanol at about 23°C. Zein (26.5 g) was added, and the resultant mixture was allowed tostir for 2 hours. 15.89 g of a 50% aqueous sodium hydroxide solution wasadded to 237.8 g of water, the resultant diluted sodium hydroxidesolution was added to the isopropanol/zein mixture, and the resultantmixture was allowed to stand for 6 hours. Sodium chloride (0.159 g) wasthen added, also with stirring. The resultant mixture was then allowedto stand for an additional 2 hours. S-type hydrated lime (1.58 g) wasthen added with stirring, and the resultant mixture was stirred untiluniform. The solids were allowed to settle, and the supernatant wasdecanted to provide the illustrative aqueous composition as the decantedsupernatant.

In a glass vessel, (2.5 g) of the aqueous composition prepared asdescribed in paragraph [0256] was combined with water (47.5 g) toprovide an extractant. Coal tar sand (5 g, 15 wt % coal tar) from aNorth Carolina gasification plant site was added to the extractant. Theresultant mixture was stirred using a magnetic stir bar for 90 minutesat about 23° C. Extraction of the coal tar from the coal tar sand wasobserved.

This example demonstrates that an illustrative Composition of theInvention is useful for extracting coal tar from coal tar sand.

Example 27

A comparative composition comprising a polysaccharide, but notcomprising plant material, was prepared as follows. Guar gum (1.978 g),citric acid (0.086 g), 15.89 ml of 70% isopropanol, sodium chloride(0.159 g), S-type hydrated lime (1.58 g) and 15.89 g of a 50% aqueoussodium hydroxide solution were added to 237.8 g of water at about 23° C.The resultant mixture was stirred until uniform.

In a glass vessel, (2.5 g) of the comparative composition prepared asdescribed in paragraph [0259] was combined with water (47.5 g) toprovide a test extractant. Coal tar sand (5 g, 15 wt % coal tar) from aNorth Carolina gasification plant site was added to the test extractant.The resultant mixture was stirred using a magnetic stir bar for 90minutes at about 23° C. No extraction of the coal tar from the coal tarsand was observed.

The embodiments described herein and illustrated by the foregoingexamples should be understood to be illustrative of the presentinvention, and should not be construed as limiting. On the contrary, thepresent disclosure embraces alternatives and equivalents thereof, asembodied by the appended claims. Each reference disclosed herein isincorporated by reference herein in its entirety.

1. An aqueous composition comprising: a mixture obtained by (a) allowingwater in an amount of about 10 wt % to about 95 wt % of the aqueouscomposition, corn gluten meal in an amount of about 1 wt % to about 50wt % of the aqueous composition, and an inorganic base in an amount ofabout 0.5 wt % to about 15 wt % of the aqueous composition to (i) stirat about 10° C. to about 100° C. for about 2 hours to about 4 hours or(ii) stand at about 10° C. to about 100° C. for about 10 minutes toabout 8 hours, and (b) removing undissolved solids from the mixture; 0%to about 10 wt % of an alcohol; 0% to about 10 wt % of an organic orinorganic salt; 0% to about 10 wt % of an organic or inorganic acid; and0% to about 10 wt % of an additive; wherein the aqueous composition hasa pH of about 13; the alcohol is a C₁ to C₃ alcohol, a glycol, a glycolether, an aminoalcohol or an aromatic alcohol; the additive is adetergent, a surface tension modifier, a flocculant, a dispersant, arheology modifier or an emulsifier; and the inorganic base is sodiumhydroxide, lithium hydroxide or potassium hydroxide.
 2. (canceled) 3.(canceled)
 4. (canceled)
 5. The aqueous composition of claim 1, whereinthe alcohol is ethanol, methanol, or isopropanol.
 6. (canceled)
 7. Theaqueous composition of claim 1, wherein the salt is sodium chloride,potassium chloride, calcium chloride, magnesium chloride, ammoniumchloride, sodium bromide, potassium bromide, calcium bromide, magnesiumbromide, ammonium bromide, sodium iodide, potassium iodide, calciumiodide, magnesium iodide, ammonium iodide, sodium sulfate, potassiumsulfate, calcium sulfate, magnesium sulfate, ammonium sulfate ormixtures thereof.
 8. The aqueous composition of claim 1, wherein theacid is citric acid, formic acid, ascorbic acid, acetic acid, malicacid, adipic acid, tannic acid, lactic acid, fumaric acid, or mixturesthereof.
 9. The aqueous composition of claim 1, wherein the additive isType S Hydrated Lime. 10.-72. (canceled)
 73. The aqueous composition ofclaim 1, wherein the mixture is obtained by allowing water, corn glutenmeal and the inorganic base to (i) stir at about 10° C. to about 100° C.for about 2 hours to about 4 hours and (ii) stand at about 10° C. toabout 100° C. for about 10 minutes to about 8 hours.
 74. The aqueouscomposition of claim 1, wherein the corn gluten meal is suspended orsubstantially dissolved in the mixture.
 75. The aqueous composition ofclaim 1, further comprising a substrate.
 76. The aqueous composition ofclaim 75, wherein the substrate is soil, sand, beach sand, oil sand,heavy-oil sand, rock, wood, paper, skin, water, gravel, mud, clay,plant, hair, fabric, class, porcelain, concrete or metal.
 77. Theaqueous composition of claim 75, wherein the substrate contains or hason its surface a hydrocarbon-containing substance.
 78. The aqueouscomposition of claim 77, wherein the hydrocarbon-containing substance isgrease, oil, heavy oil, crude oil, refined oil, shale oil, bitumen, coaltar, synthetic oil, automotive oil, oil from oil sand, oil obtained fromhydraulic fracturing, oil from the skin of an animal or natural gasliquid.
 79. An aqueous composition comprising: a mixture obtained by (a)allowing water in an amount of about 10 wt % to about 95 wt % of theaqueous composition, corn gluten meal in an amount of about 1 wt % toabout 50 wt % of the aqueous composition, and an inorganic base in anamount of about 0.5 wt % to about 15 wt % of the aqueous composition to(i) stir at about 10° C. to about 100° C. for about 2 hours to about 4hours or (ii) stand at about 10° C. to about 100° C. for about 10minutes to about 8 hours; 0% to about 10 wt % of an alcohol; 0% to about10 wt % of an organic or inorganic salt; 0% to about 10 wt % of anorganic or inorganic acid; 0% to about 10 wt % of an additive; and asubstrate that contains or has on its surface a hydrocarbon-containingsubstance; wherein the aqueous composition has a pH of about 13; thealcohol is a C₁ to C₃ alcohol, a glycol, a glycol ether, an aminoalcoholor an aromatic alcohol; the additive is a detergent, a surface tensionmodifier, a flocculant, a dispersant, a rheology modifier or anemulsifier; and the inorganic base is sodium hydroxide, lithiumhydroxide or potassium hydroxide.
 80. The aqueous composition of claim79, wherein the alcohol is ethanol, methanol, or isopropanol.
 81. Theaqueous composition of claim 79, wherein the salt is sodium chloride,potassium chloride, calcium chloride, magnesium chloride, ammoniumchloride, sodium bromide, potassium bromide, calcium bromide, magnesiumbromide, ammonium bromide, sodium iodide, potassium iodide, calciumiodide, magnesium iodide, ammonium iodide, sodium sulfate, potassiumsulfate, calcium sulfate, magnesium sulfate, ammonium sulfate ormixtures thereof.
 82. The aqueous composition of claim 79, wherein theacid is citric acid, formic acid, ascorbic acid, acetic acid, malicacid, adipic acid, tannic acid, lactic acid, fumaric acid, or mixturesthereof.
 83. The aqueous composition of claim 79, wherein the additiveis Type S Hydrated Lime.
 84. The aqueous composition of claim 79,wherein the mixture is obtained by allowing the water, corn gluten mealand the inorganic base to (i) stir at about 10° C. to about 100° C. forabout 2 hours to about 4 hours and (ii) stand at about 10° C. to about100° C. for about 10 minutes to about 8 hours.
 85. The aqueouscomposition of claim 79, wherein the corn gluten meal is suspended orsubstantially dissolved in the mixture.
 86. The aqueous composition ofclaim 79, wherein the substrate is soil, sand, beach sand, oil sand,heavy-oil sand, rock, wood, paper, skin, water, gravel, mud, clay,plant, hair, fabric, class, porcelain, concrete or metal.
 87. Theaqueous composition of claim 79, wherein the hydrocarbon-containingsubstance is grease, oil, heavy oil, crude oil, refined oil, shale oil,bitumen, coal tar, synthetic oil, automotive oil, oil from oil sand, oilobtained from hydraulic fracturing, oil from the skin of an animal ornatural gas liquid.